TWI460230B - Flame retardant polyamide compositions - Google Patents

Description

Flame retardant polyamine composition

The present invention relates to a flame retardant composition, and more particularly to a flame retardant polyamide composition which improves flame retardancy.

In the fields of printed circuit boards, heat-resistant adhesive tapes, and electrical and electronic components, flame retardant compositions are widely used as protection or interlayer insulation. At present, many thermoplastic polyamines are used as plastic materials, and other main products such as flame retardants, stabilizers and additives are the main flame retardant compositions. Among them, the various physical properties of PA6T nylon are the most attractive, but alone. The use of PA6T nylon is often caused by its melting point and decomposition temperature, which is difficult to process. Therefore, most of the current manufacturers use other nylons (such as PA66, PA6I, etc.), and the copolymers produced by blending PA6T nylon are mostly used. By using the flame retardant polyamine composition to produce products in these fields, it can have better effects of high temperature resistance, low absorption, flame retardancy and easy processing.

In the past, in order to obtain the flame retardant polyamine composition, it is preferable to have a flame retardant, and in addition to adding a flame retardant to the plastic material, the ruthenium-containing compound is used as a main additive, thereby transmitting the ruthenium-containing compound. Add a boost to the flame retardant effect. However, most of the antimony-containing compounds have environmentally incompatible toxicity, which is easy to accumulate in the ecological environment, causing adverse effects and causing nature to be in a crisis of chronic poisoning; even, the antimony compound is incompatible with bromine. When the casting film is formed, a large amount of gas is easily generated to cause deposition of the cast film, thereby blocking the feasibility of continuous production of the cast film.

To this end, the industry has devote efforts to develop other components that are sufficient to replace the ruthenium-containing compound in order to improve the above disadvantages and to maintain better flame retardancy. For example, the Republic of China Announcement No. I308168 "Flamemic Polyamide Composition and Its Use" patent case discloses a kind of 10~80% polyamide, 5~40% flame retardant, 0.5~10% a flame retardant polyamine composition composed of zinc borate and at least one other zinc salt, 0 to 60% of an inorganic reinforcing material, and 0 to 5% of an anti-drip agent, wherein the at least one other zinc salt system It is zinc phosphate, zinc stannate or calcium zinc molybdate. By adding zinc borate and at least one other zinc salt, it can replace the conventional ruthenium-containing compound, avoid most problems of the ruthenium-containing compound, and provide characteristics of flame retardancy, toughness and melt fluidity, and is suitable for electrical, Manufacturing of electronic components.

Although the conventional patent case can replace the ruthenium-containing compound with the zinc borate to solve the environmental pollution, the flame retardant effect of adding zinc borate alone is far less than that of the ruthenium-containing compound. For this reason, in the conventional patent case, it is necessary to further mix zinc salts of different proportions in the zinc borate to enhance the flame retardant effect of the composition, so that the following problems are derived.

Since the addition of additional zinc salt not only causes the cost burden of the operator, but also because the effect of each zinc salt addition is different, it takes more time to select the appropriate zinc salt and mix it with an appropriate ratio. Only then can it show better flame retardancy, so the cost and time required for relative use will become a major problem for subsequent application in product development.

In addition, if the choice of the zinc salt and its ratio with the zinc borate produces an error, the flame retarding effect of the composition is inconsistent, and even due to the excessive addition of other zinc salts, it is generated between the other components. The barrier of compatibility can not only change the flame retardant properties of the composition, but also seriously affect the physical properties of the composition itself such as strength, folding resistance, viscosity, etc., which leads to the quality of the subsequently manufactured product. consider.

In view of the above, it is indeed necessary to re-develop a flame retardant polyamide composition which is sufficient to completely replace the ruthenium-containing compound to achieve better flame retardancy to completely solve the various problems as described above.

The main object of the present invention is to improve the above disadvantages to provide a flame retardant polyamide composition which maintains the physical properties of the composition itself and relatively enhances the flame retardant properties of the composition.

A second object of the present invention is to provide a flame retardant polyamine composition which is capable of eliminating environmentally incompatible toxicity to avoid adverse effects on the environment.

Still another object of the present invention is to provide a flame retardant polyamide composition which can be applied to continuous product production to improve production efficiency.

In order to achieve the above object, the flame retardant polyamine composition of the present invention comprises: 35 to 55% by weight of polyamine, 15 to 25% of a halogen-based flame retardant, and 1 to 6%. Zinc compound, 0.2~5% epoxy resin and 10~30% adjuvant.

Wherein, the oxime resin in the flame retardant polyamine composition is composed of 77.4 to 94.6% by weight of a fluorinated resin, and 12.6 to 15.4% of cerium oxide is mixed; the polyamine is a weight. Percentage of 42.5 to 47.5% of PA6T/66 high temperature nylon; the halogen-based flame retardant is 18 to 21% by weight of brominated polystyrene; the zinc compound is 4.5% by weight of zinc borate; The adjuvant system can be selected from glass fiber, carbon fiber or talc.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

The flame retardant polyamine composition of the present invention is mainly composed of 35 to 55% by weight of polyamine, 15 to 25% of halogen-based flame retardant, 1 to 6% of zinc compound, and 0.2 to 5% by weight. It is composed of a silicone resin and 10 to 30% of an adjuvant. By the addition of the epoxy resin, the combustion characteristics of the flame retardant polyamide composition are improved, and the preferred physical properties of the flame retardant polyamide composition itself are maintained.

The polyamine can be selected as a modified PA6T nylon, or a copolymer formed by blending other nylons with the PA6T nylon (such as high temperature nylon such as PA6T/66, PA6T/6I or PA6T/DT). Because the melting point and decomposition temperature of PA6T nylon are too close, which makes the processing difficult, the present embodiment preferably uses PA6T/66 nylon as the plastic material, and it is preferably 42.5~47.5% by weight percentage. The PA6T/66 nylon series was purchased from Taiwan Plastics Co., Ltd. Therefore, the polyamine of the present invention not only has the characteristics of high temperature resistance, easy molding, but also has low absorption property of PA6T/66 nylon, so that it can improve the excessive heat absorption of the finished product when the product is subsequently produced, and the product is heated and expanded. Problems such as dimensional distortion.

The halogen-based flame retardant may be selected from brominated polystyrene, polybrominated styrene or brominated polyphenylene ether. In this embodiment, brominated polystyrene is preferably used as a flame retardant, and the weight thereof is based on the weight. The percentage is preferably from 18 to 21%, and the brominated polystyrene is purchased from Saytex, whereby the flammability of the polyamide can be lowered by the halogen-based flame retardant. Among them, the halogen-based flame retardant is selected only to achieve the above-mentioned effects, so as to lower the combustibility of the polyamide, and thus it is not limited to the brominated polystyrene of the present embodiment.

The zinc compound may be selected from zinc borate, zinc phosphate, etc., in this embodiment, zinc boronate is preferably substituted for the conventional cerium-containing compound, and the chemical formula thereof is 2ZnO‧3B ₂ O ₃ ‧3.5H ₂ O, and the zinc borate is The weight percentage is preferably 4.5% and is available from Rio Tinto BORAX. Therefore, the addition of the zinc borate can not only solve the problem caused by the deposition of the cast film, but also eliminate the environmental hazard derived from the traditional bismuth-containing compound, achieve the effect of environmental protection and improve production efficiency; even, the zinc borate can be During the heating and combustion, crystal water is generated to lower the heat of combustion and temperature to enhance the flame retardant effect of the flame retardant polyamide composition.

Herein, the polyamine, the halogen-based flame retardant, and the zinc compound are essential components of the flame-retardant polyamine composition, and each component has a mutual auxiliary function to reduce combustion heat and improve It is difficult to burn, easy to process and has no ecological and environmental hazards. However, the basic components are those skilled in the art, and can be implemented according to their functions. Therefore, they are not limited to the parts selected in the present disclosure, and will not be further described herein.

The flame retardant polyamine composition of the present invention mainly transmits the flame retardant polyamine composition by the addition of the epoxy resin without changing the physical properties of the flame retardant polyamide composition itself. Has better combustion characteristics. More specifically, the oxime resin is a polymer between organic and inorganic having a chemical formula of [R ₂ SiO] _n wherein the R is methyl, ethyl or phenyl. Depending on the length of the oxime bond skeleton, the type of the organic group, and the crosslinking between the organic group and the oxime bond skeleton, a variety of different properties and compositions of the oxirane resin can be produced, and the oxirane resins have Common characteristics such as thermal stability, water repellency, low chemical activity, and strong antioxidant capacity. Thereby, through the characteristics of the epoxy resin, the low chemical property is not easy to continuously burn with oxygen, and has the characteristics of better thermal stability, and assists the basic composition of the flame retardant polyamide composition. The effect of the flame retardancy of the composition of the present invention is relatively improved. In the present embodiment, the oxime resin added to the flame retardant polyamide composition is preferably composed of 77.4 to 94.6% by weight of cerium oxide mixed with 12.6 to 15.4% cerium oxide. In particular, an epoxy resin pellet of the type RM4-7051, which is commercially available from Dow Corning, is selected and contains 86% of an epoxy resin and 14% of cerium oxide. Further, the amount of the epoxy resin added to the flame retardant polyamide composition is suitably 0.2 to 5% by weight, and if the amount of the epoxy resin is more than 5%, the ruthenium is likely to be caused. The compatibility of the oxyresin with the polyamide is lowered, and the physical properties of the flame retardant polyamide composition itself are changed so that the subsequent quality of the composition cannot be obtained and the processing efficiency is not obtained.

Further, the flame retardant polyamine composition of the present invention may further contain 10 to 30% of an auxiliary agent, thereby enhancing the moldability of the flame retardant polyamide composition and simultaneously enhancing the flame retardant polyfluorene. The mechanical properties of the amine composition such as tensile strength and flexural strength, and the relative heat resistance of the finished product. In this embodiment, glass fiber, carbon fiber or talc may be selected as an auxiliary agent, especially glass fiber, but this embodiment only provides a preferred choice and is not limited thereto.

In order to confirm that the flame retardant polyamine composition of the present invention can pass through the addition of the epoxy resin, it has better flame retardancy without affecting the physical properties of the flame retardant polyamide composition. The different ratios of the epoxy resin were added to the flame retardant polyamide composition to observe the physical properties and UL combustion characteristics as shown in Table 1, and the results are shown in Table 1.

Among them, the detection of UL combustion characteristics is based on the UL-94 specification, and the vertical burning test is performed to form the following six different types of flame retardant polyamine compositions, each of which is formed to have a thickness of 1/16 mm and 1/32 mm. The test piece is fired separately under a condition of 10 seconds for one cycle, and then removed, and the time during which the flame is continuously burned for the test piece is measured.

In addition, the other physical property test of the flame retardant polyamine composition of the present invention includes tensile strength, flexural strength, impact strength, Rockwell hardness and shear viscosity, and the test methods of the physical properties are This field can be easily thought of by ordinary people, so it will not be repeated here.

From the results of the above Table 1, it was found that the UL combustion characteristics measured failed when the epoxy resin was not added, indicating that the flame retardant polyamine composition without the addition of the epoxy resin was significantly insufficient in flame retardancy. After adding the epoxy resin, it can be seen that the number of UL combustion seconds tends to decrease, and even when the epoxy resin is added to 3% or more, the test piece removed by flame combustion only maintains a flame of about 6 seconds. The burning time is maintained, and the shear viscosity can be maintained at a preferred value without causing troubles in subsequent processing. However, when the amount of the epoxy resin added is more than 3%, the physical properties of the flame retardant polyamide composition are easily changed, so that the tensile strength and the flexural strength of the flame retardant polyamide composition are The bending factor is significantly reduced.

Therefore, in order not to affect the physical properties of the flame retardant polyamide composition, it is possible to have better flame retardant properties at the same time, preferably 0.5% of the epoxy resin is added to reduce UL combustion. The number of seconds enhances the flame retardant properties of the flame retardant polyamide component, ensuring that the flame retardant polyamine composition can be molded to have high temperature resistance, flame retardancy, etc. In the high temperature environment such as electrical and electronic equipment, the durability and safety of the finished product are improved; even, the physical properties of the flame retardant polyamide composition are maintained to pass appropriate tensile strength, flexural strength, hardness, etc. In the subsequent production of finished products, it can have better processing properties and achieve the effect of improving production efficiency.

The flame retardant polyamine composition of the present invention is capable of maintaining the physical properties of the composition itself and achieving the effect of relatively enhancing the flame retardant properties of the composition.

The flame retardant polyamine composition of the present invention is capable of eliminating environmentally incompatible toxicity to achieve the effect of avoiding adverse effects on the environment.

The flame retardant polyamine composition of the present invention is capable of applying the composition to a continuous product production to achieve an effect of improving production efficiency.

While the invention has been described in connection with the preferred embodiments described above, it is not intended to limit the scope of the invention. The technical scope of the invention is protected, and therefore the scope of the invention is defined by the scope of the appended claims.

Claims (10)

A flame retardant polyamine composition comprising: 35 to 55% by weight of polyamine, 15 to 25% of halogen-based flame retardant, 1 to 6% of zincate, 0.2 to 5% Oxygenated resin and 10~30% adjuvant. The flame retardant polyamine composition according to claim 1, wherein the flame retardant polyamine composition is a cerium oxide resin of 77.4 to 94.6% by weight, mixed with 12.6~15.4% of cerium oxide. The flame retardant polyamine composition according to claim 3, wherein the flame retardant polyamine composition is a dope resin of Dow Corning RM4-7051, which is The percentage by weight of 86% of the oxime resin is compounded with 14% of the oxidized system. The flame retardant polyamine composition according to claim 1 or 2, wherein the polyamine is PA6T/66 high temperature nylon. The flame retardant polyamine composition according to claim 1 or 2, wherein the polyamine is 42.5 to 47.5% by weight. The flame retardant polyamine composition according to claim 1 or 2, wherein the halogen-based flame retardant is brominated polystyrene. The flame retardant polyamine composition according to claim 1 or 2, wherein the halogen-based flame retardant is 18 to 21% by weight. The flame retardant polyamine composition according to claim 1 or 2, wherein the zinc compound is zinc borate. The flame retardant polyamide composition according to claim 1 or 2, wherein the zinc compound is 4.5% by weight. The flame retardant polyamine composition according to claim 1 or 2, wherein the auxiliary agent is glass fiber, carbon fiber or talc.