TW472071B - Non-halogen fire retardant and its polyolefin resin composite and a compounding process for the polyolefin resin composite - Google Patents

Abstract

The invention relates to a non-halogen fire resistant polyolefin composite. The composition contains (1) 100 weight part of polyolefin resin and (2) 15 to 60 weight part of non-halogen fire retardant material. The said non-halogen fire retardant material includes (a) expandable graphite (b) phosphorus contained plasticizer (c) inorganic phosphode and (d) Borate. The invention also develops a processing method to keep the expandable graphite intact, prevent the expandable graphite been damaged, thus keep the fire protecting ability. The non-halogen fire resistant polyolefin resin composite can be use in electric equipment, vehicles, architecture etc. The characteristics of this composite are not only fire resisted but also low smoke, no corrosive or toxicgas emission and non-dripping during firing.

Description

: 7207.

[Field of the invention]-The present invention relates to a kind of non-letter flame retardant polyolefin resin composition and :: processing method, especially a «hydrocarbon that does not generate a large amount of black smoke or mother gas when burning. Resin-like resin composition and a processing method that effectively maintains the integrity of the expandable graphite 'so as not to be blocked by the twin-screw granulation equipment during the M process. [Background of the invention] Polyolefins and other high-molecular polymers are not used in everyday life, such as wires, electrical insulation coatings, external or i appliances, internal panels or interior, Interior materials—some building materials or furniture ... Because of the wide range of uses and plastic materials that everyone will come into contact with U: Tinan for its safety ’, it ’s difficult to handle this type of polymer products. Commonly used flame retardants are gas or wave-producing "flammables", or inorganic fillers that release H20 or CO2 ^ Although flame retardants containing gas or bromine are used, the flame retardant effect Quite wrong, but this type of flame retardant will produce a large amount of radon during processing or combustion ... especially the large amount of dense smoke generated during combustion will hinder escape. In addition, tooth flame retardants In the process of flame-resistant products, U ’s rotten acid and rotten tooth decay! Insect machines, indirectly increasing the cost of operators. Use of hydroxide, hydroxide, or carbonate inorganic materials to reduce the flammability by the production of H2 (f C〇2 (such as JP-A-Sho w_i654 3 No. 7 ^: and JP-A-Sho 6 1-3 6 3 4 3 (Disclosed in the bulletin) to achieve the purpose of flame retardancy. Reverse flame retardants do not have the disadvantages of flame retardants. However, in order to achieve the flame retardant effect, the amount of addition-generally quite large, usually More than the name. Accompanying is the financial quality of the polymer composition. 297 # i

----------- .. installed! (Please read the precautions on this page before filling out this page)-Postponing ... 4720 ?! A7 B7 5 Description of the invention (top) = worsening, greater specific gravity. The characteristics of polymer materials are light and strong. Because two = organic flame retardants achieve the purpose of flame resistance, but also destroy the high score, other toothless flame retardants have been proposed, such as organic Naif or ^ poor compatibility (such as organic Phosphoric acid, etc.), (such as osmium, polygalactose). In the industrial sector, the use of expandable graphite that has not yet been developed by Mengping to arsenic as a flame retardant for plastic materials has been proposed in the No. M public and newspaper. Graphite is used in clay resin to increase the flame-resistant effect. However, because of the serious scattering of graphite powder after swelling during burning, it is not Si :: So Jishikai Kaizhao 2 75 1 38 bulletin mentions that poly-smoky resin and expandable film have caused the flammable group to burn. Resin 'but it must be handled carefully when used. Report, = Γ: Tiger Bulletin = use expandable graphite, and then compound other resistance =, :: :: M natural polymer resin material. In addition, Japanese Patent Application Laid-Open No. 1: :: Expandable graphite and many different types:: Multiplication: Effect 'can be made into a flame-resistant polymer resin material Γί' Japanese Patent Application Laid-Open No. 8-217910 + Expandable intestinal graphite and polyphosphoric acid are added to the thermoplastic tree mouth; the flammable composition has better chemical stability, less ^: Cheng's difficulty bl ^ 5476 and JP Kaiping, etc. National Standard (CNS) A4 Specification (2i ^ Ti ^ 4? F)-" Road A7 V. Description of the Invention (Even Expandable # 7: ® t can be made according to i 2, the mixed use of fuel materials has multiplication There are many types of effects, and the flame retardant mechanism returns :: == material. But the best flame retardant effect of the flame retardant raw materials is paid; f is not the same. °. Therefore, the polymer resin materials of different flame retardants are mixed with ink to make them with high flame resistance (丄 flame retardant technology is recommended to use 2. ~ 2 .. diameter of expandable graphite 22). Graphite .: In practice, 'if fine-grained kneading effect is used, but due to expandable stone binocular', it can obtain better. , The flame retardant effect is also poor. ^ Particles from a relatively small, swelling ratio of larger expandable stone trr better flame retardant effect and the disadvantages of selecting particles to deteriorate the physical properties. Single; for; = mesh, it is easy to produce mixing Uneven, with high kneading ability 'usually mined-come, large particles are swellable ;: snail #granulation and extrusion equipment; so small particles, but also make the flame retardant; tr shear effect It will break down. Therefore, the present invention addresses the above disadvantages: ::: Excellent flammability and good non-flammability. [Summary of the invention] The main purpose of the present invention is to provide a refractory phase, Condensed-phase and gas-phase flame-retardant mechanism.-Product, which has a further purpose of the present invention is to provide a one-phase human, a polyolefin-based resin of the nature of the ancient chicken, and ""冋 Flame retardant, low smoke emission and no dripping. Another object of the present invention is to provide a ________ million method, so that the national paper standard (CNS) A_n ^ TiT (Tx, ( Please read the precautions of the arm surface before filling out this page. Employee Consumption Cooperative Seal 4720 ?! A7 V. Description of the invention (bucket) Ensure the integrity of the expandable graphite. Black, the non-flammable composition of the present invention, which includes (a) expandable stone „( b) 3 phosphorus plasticizer, and (c) inorganic phosphide, wherein the ratio of expandable " extensible graphite, phosphorus-containing plasticizer to inorganic phosphide is from 0.3 to 5.0.3 to 1.5 :, [ Detailed description of the preferred embodiment] The non-flammable non-flammable composition of the present invention includes (a) an expandable stone 'soil, (b) a phosphorus-containing plasticizer, and (ε) an inorganic phosphide. The ratio of the expandable graphite, the phosphorus-containing plasticizer, and the inorganic phosphide is 0.3 to 5: 0 · 3 to 1.5: 1. —This & No of the month _ flame retardant polyolefin resin composition, including 1GG weight part of the polyolefin resin, and 15 to 6q weight of non-flame retardant. $ This flame retardant resin composition can be first formed into plastic pellets using a twin-screw extruder t • ’East, and the plastic pellets can be suitable for injection or extrusion molding. The toothless flame-retardant composition of the present invention is a flame-retardant mechanism composed of a solid phase unbranched compound having expandable graphite and a condensed phase composed of a polyolefin resin and a gas phase three-phase co-construction with a plasticizer. Features. In addition, in order to further improve the flame retardant effect, the toothless flame retardant composition of the present invention can also add a small amount of borate, the main function is that the borate will form glassy during the combustion process. , And can make the expanded worm-like graphite difficult to fly to ensure a flame-resistant effect. This will maximize the fire and flame retardant properties. The phosphorus-containing plasticizer used in the present invention has the dual effects of flame retardance and lubrication. 'Mixed with the expandable graphite in advance, the expandable graphite can be lubricated so that the paper's scale is applicable to China's national standards. Yes _)-(Please read the notes on the back before filling out this page) Binding i-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs > 4

2. Description of the invention (S) It will not be broken by the double screw with high shear force when the money is drilled in the twin screw house M. ri. The scraping point of the ground scraper is low (some are liquid at normal temperature), and the fluidity is good. It is widely accepted, and the people are better than the flame retardant raw materials that melt quickly in the twin screw extruder. And Jiao Dan & "Yi He He Yi is mixed with polyolefin resin, so in order to ensure that the expandable graphite powder is not crushed by potential insects ^. Α and 4 ^ dry crushed, the present invention will be a phosphorus-containing plasticizer The combination of t * with the expandable graphite powder is added by the side feeder of the twin-screw extruder to obtain the best mixing and flame retardant effect. Resins refer to low-density polyethylene, linear low-density polyethylene (LLDPE), high-density polyethylene (supplied), polypropylene (PP), ethyl acetate (methylene acetate)) / ethylene acrylate copolymer (EE A), Ethylene Acrylic Copolymer (EBA), Ethyl Acrylic Copolymer (EMA), Ethylene Propylene Copolymer or any one or more of them The expandable graphite used in the present invention refers to the conventional scale-like graphite warp. Strong acids such as concentrated sulfuric acid, nitric acid, and concentrated nitric acid, peroxy acid salts, permanganates, dichromates, hydrogen peroxide, etc. Compounds are intercalated between the graphite layers after the oxidant is co-treated. For example, the neutral expansibility is paid by neutralizing treatment with alkali gold or alkaline earth compounds, and graphite is even better. As for expandable graphite The particle size is preferably greater than 80 mesh, and if the particle size is less than 8Q mesh, the lungs are not good. The use of expandable graphite with a particle size of 80% or more and 50 mesh is the best flame retardant effect. Phosphorus-containing plasticizers mentioned, such as trimethyl phosphate (MPP), triethyl 6-acetate (TEp), triphenylacetate (τρρ), triphenol phosphate (TCP), trimethyl phosphate Any one or more of phosphoric acid vinegars such as dibenzyl ester (τχρ), dibenzyl phosphate (CDP), etc. are used in combination. The size of this paper is applicable to China National Standard (CNS) A4 specification 297%) (Please read first (Please fill in this page for your attention) ---- I --— Order --------- # Ministry of Economy Production Bureau staff consumer cooperatives Innu 472071 A7 V. Description of the invention (inorganic phosphorus compounds used in the present invention refer to red phosphorus, ammonium phosphate, polyacrylic acid UPP), melamine acid (liver), melamine Pyroscale acid (MPP) and the like are used singly or in combination. The acid salt used in the present invention may be zinc borate, magnesium borate, manganese borate, sodium borate, etc. One of them is used singly or in combination. The flame retardant of the present invention The polyolefin resin composition can be added with antioxidants, fillers, antistatic agents, stabilizers, bridging agents, toners, etc. to the same extent as long as the physical properties are not hindered. The smoke resin composition is most suitable for kneading and granulation using a twin-screw extruder. The mixture of polyolefin rubber pellets, inorganic phosphides, and borate is fed from two main feeders or It is mixed in advance according to the specific order and fed from a main feeder with a feeder. The mixture of expandable graphite powder and plasticizer with a dish is fed into the rice hopper by a side feeder, and the temperature of each section is set to not more than 20 (TC is appropriate. Or use a kneader to mix all the materials in- The single-screw extruder is used for extrusion and granulation. The temperature during the whole process should be below 200 ° C. For the convenience of further explanation, the following examples will be enumerated for a more detailed description. The following implementation The example is a specific description of the present invention, but it will not be the scope of the present invention. Different types of fluorenes and fats and the material barrier composition disclosed in the present invention are produced by Shuanger according to different proportions, and the composition is mixed to dust. Granulate into toothless flame-retardant poly (hydrocarbon) lipids from Example 7 to Example 7 (ff as shown in Table 1). Then make 1 / r and i / r test pieces with an injection machine and follow ASTM Measure the oxygen limit index and UL_94 combustion test for evaluation of flame retardancy. The results are shown in the table—show it. The paper size is applicable to the national standard (CNS) A4 specification (2). 2 Γ— Α7Β7 5. Description of the invention (9) Table 1. Proportion and combustion test results of non-letter flame retardant polyolefin resin Example 3 Example 4 Example 5 Example 6 Example 7 PP1 100 — — — — 80 70 PP2 — _ 100 — One — One LDPE — 100 — One — 10 30 EVA — — 100 10 — EBA — One — __ 100 „__ Expandable graphite 25 10 20 15 30 15 12 TPP 3 10 3 15 6 10 3 APP 5 0 10 0 20 0 8 MPP 0 27 0 25 0 15 0 Zinc borate 1 3 1 5 2 3 1 Oxygen limit index (L0I) 30 29. 5 29 30 31 28.5 28 UL-94 1/8 " V0 V0 V0 V0 V0 V0 V0 V0 UL-94 1/16 V0 V0 V0 V0 V0 V0 V2 V2. The selection of materials in the table is as follows: PP1. · Fuju 6 3 3 1, injection grade homopolymer, M I = 1 4 PP2: Fuju ST031, injection grade copolymer, MI = 1 5 LDPE: ΝΑ 2 0 8, TaiPo-II II-I II —! 1 I (Please read the precautions for your face before filling out this page) Order. Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) A4 (210 X 2979 ^ ¾) ) 472071 Α7 Β7 V. Description of the invention (S) UE 6 3 3, Taiwan Poly BOREALIS AB AP422 5 Hochest MP-2C, Guofeng Enterprise + 50mesh, > 80% National Carbon Technology ZB-467 * Great Lakes

Co .: According to the test data of Table-B, Daba Chemical Industry Co., Ltd., the resin composition containing the toothless hard object in this case has an oxygen limiting index higher than 28, and the flame resistance is evaluated by a fire test. It is difficult to burn and has high flame resistance, so from the above test, it can be seen that the resin composition containing Si ά-in addition to having fire resistance and flame retardant properties, when burning ^ smoke is low and will not produce rotten or It is a toxic gas, and it can suppress dripping of polyolefin plastics during combustion. Intellectual Property Bureau of the Ministry of Economic Affairs

EVA EBA APP MPP EG Zinc Borate TPP

Chemical

= Chen 'The present invention, regardless of its purpose, means and performance :: The characteristics of the known technology are "smoke suppressing and flame retardant compositions": broken' sincerity #Keeping inspection by members of the expensive patent committee, I would like to grant the quasi-patent 2 society ' Real sense. However, it should be noted that 'the above-mentioned embodiments are only J = for example' and the scope of the rights claimed by the present invention is based on the description of Dian Qianwei, and is not limited to the above-mentioned embodiments. Consumption and If

Claims (1)

47207 Bulletins A8 B8 C8 D8 Sixth, the scope of patent application, a non-flammable composition, which includes (a) expandable stone (b) phosphorus-containing plasticizer, and (c) inorganic phosphide; among which expandable graphite, phosphorus-containing plasticizer The ratio to the weight of the inorganic phosphide is 0.3 to 5: 0.3 to 1.5: 1. A halogen-free flame-retardant polyolefin resin composition comprising (1) 100 parts by weight of a flame-retardant polyolefin resin, and (2) 15 to 60 parts by weight as hard to expose as an applicant! Item of halogen-free flame retardant composition. 3. The halogen-free flame-retardant polyolefin resin combination unloading la * described in item 2 of the dagger range is one or more selected from the group consisting of low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), High-density polyethylene (HDPE), polypropylene, ethylene vinyl acetate copolymer (EVA), ethylene ethyl acrylate copolymer (EEA), ethylene butyl acrylate copolymer (EBA), ethylene roasted acrylic methyl acetate copolymer ( EMA) and a copolymer of ethylene and acrylic copolymers te :: machine. I ___ 4. The non-flammable composition as described in item 1 of the SililS range, where # 测 职 历 I ink is 20 mesh to 2 0 0 mesh natural flaky graphite or an interlayer intercalation process to produce an expandable with thermal expansion characteristics 5 · The non-correspondence flame retardant composition as described in item 1 or 4 of the SSLil range, its production_ 涵 丨 | Ink is a kind of neutral swellable graphite whose particle size is greater than 50 mesh: · Pan age group (above. 6) As halogen-free flame retardant composition as described in item 1 of the iSteaj range, this paper size applies Chinese national standards (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) _ 装 _ .11 · Ministry of Economic Affairs Printed by the member of the Intellectual Property Bureau Η Consumer Cooperative 472071 A8 B8 C8 D8 6. Scope of patent application (please read the notes on the back before filling this page) where the inorganic phosphide is one or more selected from the group consisting of Honglu, acid filling, polyphosphoric acid A group consisting of ammonium, melamine phosphoric acid, and melamine pyrophosphate. 7. The halogen-free flame-retardant composition as described in item 1 of the barrier range, wherein the valley: phosphorus " Ester (TMP), Triacetic Acid Phosphate (TEP), Triphenyl Phosphate (TPP), Triphenol Phosphate (TCP), Tris-Dimethyl Phenyl Phosphate (CDP) 8. The toothless flame retardant composition according to item 1 of the scope, further comprising: fiber: borate of deafness vitreous phase. 9. The halogen-free difficulty as described in item 1 or 8 of the scope Combustion composition, education and education: Township class is one or more selected from the group consisting of pendant acid, magnesium pentamate, and Wei Li'an acid. 10. As described in item 1 or 8 of the scope The halogen-free flame retardant composition, Na Na! The amount of salt added is less than 10% of the total weight of the toothless flame retardant composition. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 11. A method for processing flame-retardant resins, characterized in that expandable graphite is mixed with a phosphorus-containing plasticizer in advance, and fed by a side feeder of a twin screw machine ; Resin and inorganic scale can be fed from the main inlet with two feeders respectively, or after the resin and inorganic stone compound are pre-mixed ', the main + is fed by one feeder, and double "Screw Extruder A" "Kun Lian 敕 〖.〗 4 + Γ ~, not more than 2.乂 is the temperature setting of each section of the 1 'press machine. This paper size is applicable to the national standard (CNS) A4 specification (2j〇 X 297 mm). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. Scope of patent application 12. The processing method described in item 11 of the scope of _11 times_, where the dosage of the inorganic phosphide and phosphorus-containing plasticizer in the expandable building and The weight ratio of the resin substrate is from 0.05 to 0.5: 0.1 to 0.1, 5: 0. 0.3 to 0.15: 1. (Please read the precautions on the back before filling this page.) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 4