TW200424254A - Formulation and manufacturing method of polyolefin open-pore foamed material - Google Patents

Abstract

A formulation and a manufacturing method of polyolefin open-pore foamed material are provided. A polyolefin material, a foaming agent, a foaming aid, a cross-linker and hollow glass beads, according to the formulation proportion, are mixed into a mixture, which is followed by heating, molten blending, sheet forming and weighing. The weighed resin material is placed into a mold cavity and the mold is heated up to a temperature higher than reaction temperature of the foaming agent and the cross-linker to performing a foaming process. The open-pore foamed material is obtained after the cross-linking and foaming process of the resin material is completed and the mold is opened up.

Description

V. Description of the invention (1) [Technical field to which the invention belongs]... The present invention is a compound of 1 type of polyolefin open-cell foaming material, and a manufacturing method t, especially a type that makes polyolefin smoke open. Formula for dyeing environment and its manufacturing method. Ho tf's personalization [Prior technology] k / Press ‘open-cell foaming material can produce capillary phenomenon for use as = :, Lu: the characteristics of cell connectivity’ and so on. And this material is private; water-absorbing materials, filter materials and breathable materials are punched, insulated, sound-absorbing and quality; =, so both; breathable, soft, and slowly in the following various products :, inch Use to make 1 · Use open-cell foam materials to show ^ characteristics, and be used as insoles or tongues ^ have wind, cushioning, softness and light weight, etc. 2 · Use open-cell foam materials and characteristics, as sound-absorbing insulation: materials, Sound absorption and cushioning (anti-vibration) 3 · Using open-cell foaming :::: or a speaker frame or a film frame. As a seat cushion, pillow, -2 "has softness, cushioning and light weight characteristics, it is easy to take in autumn, knees, cushions and handles are clumsy. It is difficult, because the formula and manufacturing process of the foam material are quite complicated. 5, US Patent No. 5 ^ Preparation method of open-cell foaming material and: Preparation method of foam material and No. 2 7 6 discloses an open-cell two-porosity (density 0.03 ~, and if it is to reach 9 0% or more ^ i 2 ϊ ^ #] ^ ^ ^ ^ ^ # ^ ^, ten go to kill $ 洎 _ to enter the pressure change foam, and finally have to, though, before] above Γ190 ... happy. Reveals the polyolefin open-cell foaming material V. Description of the invention (2) Preparation method of the material and its formula, and 1. Complex manufacturing process: ~ In order to improve the foaming material, a specially designed needle bed or two lifts are opened. Porosity, operation and maintenance of such a needle bed gas are not easy. 5 2 · Process is time-consuming and costly: Explosive materials need to be extruded first, which will lengthen the entire machine and other peripheral equipment, which will increase 3 · Environmental pollution: The aforementioned technology requires dilute coupling agent with> cereal in polyolefin smoke. Injection of solvent volatilization and recovery will create 4 • Energy consumption: The aforementioned technology has an extra step in the process of manufacturing open-cell high-foaming process, grafting a silane coupling agent (not only resulting in increased process costs, but also in view of the above-mentioned many disadvantages, The practice of plastic foam processing has been modified, and a formula and method for making foam can be proposed. [Inventive Content] 仍 The following disadvantages still exist: $ 率 'needs to be foamed after foaming The material net is used to puncture the cells, so that it is costly to set up needles and other injuries, and the needle bed process is made of coupling agent grafting technology, which is more & day guard and additional cost of extruding equipment must be added. In terms of branching technology, usually the extruder is a problem of environmental pollution in such a process. In the process of foaming materials, it is more common than extruding the hydrocarbon material to the extruder first, including the step of needle sticking at the back) No energy is consumed. The inventor has carefully considered and tested for many years. 'After countless experiments and material selection, the open hole development has overcome the various disadvantages mentioned above.

V. Description of the invention (3) The main purpose of the present invention is to solve the above problems and provide a formula for polyolefin open-cell foamed materials and a method for manufacturing the same. By adding 10 to 30 phr of hollow glass spheres to the formula In order to simplify the process, reduce the pollution to the environment, and achieve the effect of increasing the open porosity, the foam that was originally independent bubbles can be transformed into a material with open cells. To achieve the foregoing objectives, the formulation of the polyolefin open-cell foam material of the present invention includes:

a · Polyhydrocarbon material 100h r; b · Foaming agent 2 ~ 25phr; c · Foaming assistant 0 · 3 ~ 8 · 0 phr; cl · Slip agent 0 · 2 ~ 1 · 5 phr; e · Bridging agent 0 · 3 ~ 2 · 0 phr. f. Hollow glass ball 10 ~ iBOphr. The method for manufacturing a polyolefin open-cell foaming material of the present invention includes the following steps: a. Mixing and stirring the polyolefin material with a foaming agent, a foaming assistant, a bridging agent, and a hollow glass ball in proportion to form a mixture; b. The mixture is heated and melted and kneaded at a temperature above the melting point of the polyolefin to form a uniform kneaded compound; c. The uniform kneaded compound is made into a sheet shape, and the weights are stacked according to the size of the foaming cavity and stacked separately; and d · Put the weighed rubber compound into the cavity, heat the mold to a temperature higher than the reaction temperature of the foaming and bridging agent, and then open the mold after the rubber is completely bridged and foamed to obtain open-cell foaming. material.

Page 7 V. Description of the invention (4) The above and other objects and advantages of the present invention can be easily understood from the detailed description and drawings of the selected 4 embodiments below. Of course, the present invention allows some differences in the arrangement or arrangement of other parts, but the selected embodiment is described in detail in this specification and its structure is shown in the drawings. [Embodiment] Please refer to FIG. 1. The steps shown in the figure are selected steps of the embodiment of the present invention. This is for illustration purposes only and is not subject to such restrictions in patent applications. The manufacturing method of the polyolefin open-cell foaming material in this embodiment includes the following steps: a. Mixing: Mixing and mixing a polyolefin material with a foaming agent, a foaming assistant, a hollow glass ball, a bridging agent and the like to form a mixture . b. Kneading: The mixture is heated and melted and kneaded at a temperature above the melting point of the polyolefin to form a uniform kneading compound. c · Making of tablets: The uniform compounded rubber is made into a sheet shape, which is weighed according to the size of the foaming cavity and then stacked separately. d · Foaming: Put the weighed rubber compound into the cavity, heat the mold to a temperature higher than the reaction temperature between foaming and bridging agent, and open the mold after the rubber is completely bridged and foamed to obtain the openness Of foaming materials. e · Peeling:

Page 8 5. Description of the invention (5) Remove the outer skin of the foamed product. The formulation of the polyolefin open-cell foaming material developed by the present inventor includes an open-cell primary foaming formula and an open-cell secondary foaming formula, and a low-open-cell ratio formula is listed below for comparison. The following is a description of each of these three formulations and their manufacturing methods: Low porosity formula salt content Wt% & (Wonder, polyolefin material + EVA (ethylene vinyl acetate S ester *) β 100 ^ hair Foam 44 zinc oxide! Or stearin or its mixture β 〇β Hard grinding ftl (Steadc acid) ″, WV./,., .Vv > VWvWvV,, Foaming surface y Azobis If 醯ADC (ADCA) .p 1-button DCP, dicumyl peroxides Manufacturing method: a · Mix the poly (hydrocarbon) material with the foaming agent, foaming assistant, slip agent, and bridging agent according to the ratio by a mixer (Lina machine or Wanma machine ) Mix to form a mixture. B. The mixture is heated to a temperature above the melting point of the polyolefin, that is, 100 ° C to 125 ° C for 15 to 25 minutes to form a uniform compound. C. The uniform compounded rubber material is made into a sheet shape by a double roller machine, and according to the size of the foaming cavity, the ratio of the weight of the rubber material to the volume of the cavity is 1 g / cm 3 to weigh the rubber material and Stack it for future use. D. Put the weighed compound into the cavity, and heat the mold to a temperature higher than the reaction temperature of foaming and bridging agent. Perform a foaming operation between 50 ° C ~ 170 ° C, and then heat to a temperature between 165 ° C ~ 180 ° C for secondary foaming work, after the rubber is completely bridged and foamed

Page 9 V. Description of the invention (6) Opening the mold, that is to obtain an open-cell foaming material. * e · Peel, remove the outer skin of the foamed product. After testing, the physical properties of the low-porosity foamed material made by the method of the present invention are as follows: Density (g / an 3 > 0.035. ^. Hardness (Asker, 30 ~ 4. 1) 〇 < 5 ^, large pores + (< 250., water absorption (a > • 1D, Γ

In this test: The porosity is measured in accordance with the test method of ASTM D2856. The water absorption is measured in accordance with the test method of ASTM D 1 0 5 6-7 3. μ Polyolefin M material < EVA (Ethylene Acetate Acetate) ^ 100 ^ Assistance gas low zinc or zinc stearate or its mixed wheel ^ 0 < 8 ': lubricant θ hard relay iron LOp camp Bubble dance P azobis 1 methylamine test (ADCA> bridge agent ρ DCP, dicumvl peroxides L0 ^ t empty break glass ball * 15 plus

Manufacturing method: a · Mix the polyfluorene material with the foaming agent, foaming assistant, slip agent, bridging agent and hollow glass ball according to the ratio by a mixer (Lina machine or Wanhua machine) to form a mixture.

Page 10 V. Description of the invention (7) b · The mixture is heated and melted for 15 to 25 minutes at a temperature above the melting point of the polyolefin, that is, 100 ° C to 125 ° C, to form Mix the rubber evenly.

c · The uniform compound is made into a sheet shape by a double roller machine, and the compound is weighed and stacked according to the size of the cavity of the foam, and the ratio of the weight of the compound to the volume of the cavity is 1 g / cm 3 spare. d · Put the weighed rubber compound into the cavity, and heat the mold to a temperature higher than the reaction temperature between foaming and bridging agent. That is, the temperature is between 160 ° C ~ 175 ° C for one foaming operation. After completely bridging and foaming, the mold is opened to obtain an open-cell primary foamed material. e · Peel and remove the outer skin of the foamed product. After testing, the physical properties of the open-cell primary foamed material made by the present invention are as follows: dense waste (g / 'Cffi (K 0635. hardness (shoreOOO)' 62 ~ 6 core_porosity (¾ > 35 ~ Stomatal size (# 100〇 ~ ™. Water yield (1;) <. 30 ~ 321

Open cell secondary foaming formula

Page 11 V. Description of the invention (8) Salt content P heavy f first polyene transfer material < EVA (:: ethylene · vinegarSethylene S final conglomeration) p 100 ^ hairball: or hard waste Zinc or its compound # 1 plus a clearing agent ρ Continued (Steark add) # • · ·. ^ WVvWvVW ^ W ·. ^ 矣 0,8 ^ foamed azo double f turtle (ADCA) e IS. Bridge bridging μ DCP, dicumYl peroxides L2 ^ ft breaking glass ball + 15 ^ Manufacturing method: a · Polyolefin material and foaming agent, foaming aid, slip agent, bridging agent and hollow glass ball are mixed by a mixer ( Lina machine or ten-horsepower machine) to form a mixture. b. The mixture is heated and melted for 15 to 25 minutes at a temperature above the melting point of the polyalkylene hydrocarbon, that is, 100 ° C to 125 ° C, to form a uniform kneading compound. c · The uniform compound is made into a sheet shape by a double roller machine, and the compound is weighed and stacked according to the size of the cavity of the foam, and the ratio of the weight of the compound to the volume of the cavity is 1 g / cm 3 spare. d · Put the weighted compound into the phase: in the cavity. 'Heat the mold to the reaction temperature of foaming and bridging agent. That is, once the temperature is between 150 ° C ~ 170 ° C. Foaming work, and then heated to a temperature between 16 5 ° C ~ 180 ° C for secondary foaming work, after the rubber compound is completely bridged and foamed, and then open the mold, to obtain open cell secondary foaming material. e · Peel and remove the outer skin of the foamed product. After testing, the properties of the finished product of the open-celled secondary foamed material made by the present invention are as follows:

Page 12 V. Description of the invention (9) Density (g / e® 1 's-η. Hard waste (Shore ㈣Ο). 41 ~ 4 57 ^ "'-_ Porosity (M > 8δ ~ 9 ^ 7 ~ — Gas size (# 250 ~: iiMT --- Water absorption (¾ > 55 ~ 74 ^ '~ The polyolefin material used in the formulation of the foregoing embodiment of the present invention, & EVA (ethylene-vinyl acetate Ester complexes), in addition, low density polyethylene, metallocene polyethylene and combinations thereof can also be selected. And the blowing agent of the present invention is an azo series of organic foaming 胄 _ _ Azobiscarboxamide (ADCA, Azodicarbonamide or AC), in addition to this, you can also use the organic blowing agent osmium diphenyl sulfonate (P. p-〇xy ~ bi (benzenesul fony 1 hydrazide), OBSH), or a mixture of inorganic hair, sodium bicarbonate (baking soda) and citric acid, the above%, and 2 are not only good in dispersibility, but also very safe to use. At the same time, ADCA's hair & 3 The decomposition temperature of the foaming agent can be adjusted by the addition of a foaming assistant, and it is called ^ Θ. Known> The addition amount of the E agent ranges from 2 to 2 5 phr, so as to adjust The density of different foams or foams. ° + The amount of foaming additives such as zinc oxide (Z inc 0 X ide) or stearic acid (Zinc stearic acid), the range is 0.3 ~ 8pt ^, preferably in the range of 0.8 to 2.5 phr. In order to make the rubber compound easier to knead, shape or mix during processing, and not stick to the machine, stearic acid or PE wax will be added to the formula. Agent, with ^ pulling effect, and its addition range is between 0.2 · 1 ~ 5phr, preferably #full is between 0.5 ~ l.Ophr. Λ

V. Description of the invention (10) In order to make the micro warp material in the present invention form a microcellular foam structure during the foaming process, it must be managed so that the temperature of the polyolefin material is not too high during heating and foaming, resulting in viscosity Reduce and let the gas decomposed by the foaming agent escape, and can not form a microcellular foaming structure, so the peroxide (per ο X ide) commonly known as a bridging agent must be added to the formula, such as D c P (dicumy 1 peroxide) or tert-butyl cumyl peroxide, which can make the polycondensation dazzle; the viscosity of the polymer is increased to prevent the gas from escaping after foaming and decomposition. The amount of peroxide added ranges from 0.3 to 20 phr, and the preferred range is 0.5 to 1.5 phr. It should be emphasized that, in order to promote the conversion of foams that were originally independent bubbles to materials with open cells, the present invention will add ^ = 5 spheres to the formula, and in the foregoing embodiment, the hollow burst The glass ball system is composed of: Silica gas (Silica, Si02 accounts for about 50 ~ 70%) and Dioxide (Alumina, A 1 203 accounts for about 30 ~ 5, 0%) Of course, the hollow glass ball It can also be made of other ingredients. 'I have learned through continuous research by the inventors' that there are certain specifications for "hollow glass spheres" that can promote the body of the present invention to achieve open cells > because the diameter of the hollow glass spheres is too small, openings occur. Sex bubbles =. It will decrease, or even approach zero; if the particle size is too large, the above example will be larger, and the bubble framework of broken bubbles will easily collapse, making the air bubble body difficult to form. According to the research of the present inventors, the teachings of hollow glass spheres are between 12 ~ 350 micrometers (micros, #m), and the preferred range is 50 ~ 200 micrometers. The particle size distribution range The closer or narrower; the size of the open-cell bubbles formed will be more even, and the% glass hollow ball is worried

Explanation on page 14 (⑴ ^^-is in the range of 10 ~ 30 phr, and the preferred range is 14 ~ kb.) For the low-perforation hair made before, a xl,. Phr, 丄 τ:,), add a hollow The glass ball can lower the original porosity by 20, and the present invention can increase the porosity under the condition of the ratio of 5% <5%, so that the porosity is equal to r ^ 35 ~ The finished product has a pore size of 85 ~ 95%. Too ... :: The pore ratio of the foamed material is more water-proof than the low-pored foamed material 4 and the finished product of the secondary foamed material Physical properties ;, Porosity-sub-foamed glass ball

Up to 85 ~ 9 5%, the present invention is in the formulation; the effect of the material's open porosity and porosity is very significant, and can have; 2: 3 glass balls can improve: the rate, so that the formulation and manufacturing method of the present invention The expected air permeability, softness, and cushioning properties are also relatively improved. As mentioned above, compared to the conventional technology, the formulation and manufacturing method of the polyopen-cell foamed foamed material of the present invention do not need to cooperate with 2 = And can reduce the production process and reduce: made into: balls that can promote functional bubbles that originally = open porosity, and can achieve the improvement of the above-mentioned embodiment of the disclosure is C7% sundial too respectful The day w restricts the date and time of the month, so Λ number is used to indicate the day and night: for the purpose of explaining the text, Asia and Africa belong to the scope of the present invention. The replacement of Ai Geng or equivalent components should still be able to reach the previous and next 5 details, so that those skilled in the art can understand the application of the present invention: the '... patent

f Page 15 Brief description of the drawings [Simplified illustration of the drawings] Fig. 1 is a flowchart of the manufacturing method of the present invention

Page 16

Claims (1)

6. Scope of patent application: 1. A method for manufacturing a polyolefin open-cell foaming material, which includes the following steps: a. Mixing a polyolefin material with a foaming agent, a foaming auxiliary agent, a hollow glass ball and a bridging agent in proportions. Stir to form a mixture; b. The mixture is heated and melted and kneaded at a temperature above the melting point of the polyolefin to form a uniform compound; c. The uniform compound is made into a sheet and scaled according to the size of the foam cavity Stack them separately after weighting; and d. Put the weighed rubber compound into the cavity, heat the mold to a temperature higher than the reaction temperature of the foaming and bridging agent, and open the mold after the rubber is completely bridged and foamed to obtain Open-cell foam material. 2. The method for manufacturing a polyolefin open-cell foam material according to item 1 of the scope of the patent application, wherein step b is heating the mixture at a temperature of 10 (TC ~ 1 2 5 ° C for 15 ~ 2 5 minutes). Melting and mixing work. 3 · According to the manufacturing method of polyolefin open-cell foam material described in item 1 of the scope of patent application, in step c, the mixed rubber is made into a sheet shape by a double roller machine. 4 · According to the scope of patent application The method for manufacturing a polyolefin open-cell foamed material as described in item 1, wherein in step c, the rubber compound is weighed and stacked for use at a ratio of 1 g / cm 3 of the rubber compound weight to the cavity volume. 5 · According to the application The method for manufacturing a polyolefin open-cell foamed material as described in the first item of the patent scope, wherein the foaming procedure in step d includes a foaming work performed at a temperature between 150 ° C ~ 170 ° C and Secondary foaming at temperatures between 16 5 ° C and 180 ° C. Page 17 6. Scope of patent application, 6 · According to the method for manufacturing polyolefin open-cell foamed material described in item 1 of the scope of patent application, in step d, the mold is heated to 160 ° C ~ 175 ° The foaming and bridging work is performed at a temperature of C. 7. The method for manufacturing a polyolefin open-cell foam material according to item 1 of the scope of patent application, which further includes step d, peeling to remove the outer skin of the foamed product. 8 · —A kind of polyolefin open-cell foaming material formula, which includes: a · Polycarbonate material 100 phr; b · Foaming agent 2 ~ 2 5 phr; c · Foaming assistant 0. 3 ~ 8 · 0 phr; d · slip agent 0 · 2 ~ 1 · 5 phr; e · bridging agent 0 · 3 ~ 2. 0 phr. f. Hollow glass spheres 10 ~ 30phr. 9. Formulation of polyolefin open-cell foam material according to item 8 of the scope of the patent application, wherein the polyolefin material is composed of low density polyethylene, ethylene and vinyl acetate copolymers, metallocene polyethylene and combinations thereof Ethnic group. 10 · According to the formula of the polyolefin open-cell foaming material described in item 8 of the scope of the patent application, the foaming agent is an azo series organic foaming agent, such as: azobisamidine, monooxane Europium besylate. 1 1 · According to the formulation of the polyolefin open-cell foam material described in item 8 of the scope of the patent application, the foaming agent is a mixture of inorganic sodium bicarbonate and citric acid. 1 2 · Polyolefin open-cell foam according to item 8 of the scope of patent application 16. Scope of patent application The formulation of the materials, among which the foaming assistant is one of zinc stearate and zinc oxide, or a mixture of the two. 1 3 · According to the formulation of the polyolefin open-cell foaming material described in item 8 of the scope of the patent application, the preferred range of the foaming assistant is 0.8 ~ 2. 5 phr 〇1 4 · According to the scope of patent application No. 8 The formulation of the polyolefin open-cell foaming material described in the item, wherein the lubricant is one of stearic acid and PE wax. 1 5 · According to the formulation of the polyolefin open-cell foaming material described in item 8 of the scope of the patent application, the preferred range of the slip agent is 0.5 to 1. 0phr 〇1 6 · According to the scope of the patent application item 8 Formulation of polyolefin open-cell foaming materials, wherein the bridging agent is peroxide such as DCP (di cumy 1 peroxide) and tert-butyl cumy 1 peroxide. 1 7 · According to the formulation of the polyolefin open-cell foaming material described in item 8 of the scope of the patent application, the preferred range of the bridging agent is 0.5 to 1.5 phr 〇 1 8 The formulation of the polyolefin open-cell foaming material described above, in which the hollow glass spheres are composed of 50 to 70% of silicon oxide and 30 to 50% of aluminum oxide, and the particle size of the hollow glass spheres is between Between 2 and 3 50 microns. 1 9 · According to the formulation of polyolefin open-cell foam material described in item 8 of the scope of the patent application, the preferred range of hollow glass spheres is 1 4 ~ 2 2 Page 19 Page 20