KR100978777B1 - Frie-retardant core resin composition without heavy metal and non-holgen - Google Patents

Abstract

The present invention relates to a flame-retardant core resin composition containing no heavy metals and halogens, and to a method for producing a composite panel using the same. More particularly, the present invention relates to toxic bromine (Br), The flame retardant core resin composition using environmentally friendly materials without the use of halogen-based and heavy metal-based flame retardants such as chlorine (Cl) and antimony (Sb) compounds, and a method of manufacturing a composite panel using the same, supplementing the disadvantages of existing flame retardant plastics. It aims to manufacture an eco-friendly composite panel that solves the problems that are harmful to the environment and the human body.

In order to realize this, the composition of the present invention comprises a polyolefin resin, a flame retardant, a flame retardant aid, a lubricant, an antioxidant, and a polyolefin resin and a flame retardant, a flame retardant aid, a lubricant, antioxidants for producing the composition of the present invention A resin composition manufacturing step of quantitatively composing;

A core manufacturing process for preparing an internal core by putting the prepared resin composition into an extruder;

This is supplied to the hot roller (HR) in a lamination together with the metal sheet (B) and the hot melt adhesive sheet (C) and penetrates the hot roller (HR) while passing through the metal sheet (B) / adhesive layer (C) / inner core (A) / The composite panel which consists of a 5-layered structure of a contact bonding layer (C) / metal plate material (B) consists of a composite panel manufacturing process which manufactures continuously.

Polyolefin, Flame Retardant Core, Melamine Phosphate, Flame Retardant, Composite Panel

Description

Frie-retardant core resin composition without heavy metal and non-holgen}

<Description of the codes for the main parts of the drawing>

HR: hot roller

A; Internal core

B; Metal plate

C; Adhesive layer or adhesive sheet

D; Cutting device

E; Reinforcement

The present invention is to produce a flame-retardant core resin composition containing no heavy metals and halogens and composite panels using the same, halogen, such as toxic bromine (Br), chlorine (Cl), antimony (Sb) compounds in the polyolefin resin as an inner core An eco-friendly composite panel that solves the problems of environmental and human health that compensates for the disadvantages of existing flame-retardant plastics by manufacturing a flame-retardant core resin composition using environmentally friendly materials without using flame retardants and heavy metals It relates to a manufacturing method of.

In the event of a fire, the damage to human life caused by the generation of toxic gases is more serious than the damage caused by the fire itself. Therefore, research has been conducted on flame retardant plastic composite panels. , Zinc, etc.) and polyolefin-type thermoplastic resin cores filled inside, and this core is being replaced by a flame-retardant resin core in a combustible plastic composed of carbon, hydrogen, and oxygen components.

Conventional flame-retardant plastic composite panels contain halogen (Br-based, Cl-based, etc.), heavy metal-based (Sb-based), or halogen-heavy metal composite-based flame retardants, which are excellent in flame retardancy, while hydrogen bromide (HBr), which is a toxic substance at high temperature processing and combustion. ), It generates a large amount of hydrochloric acid (HCl), and in anoxic conditions, it generates serious poisonous carcinogens such as halogenated dioxins and furans, which have serious lives, property and environmental pollution. Developed countries, which already have regulations on the emission of flammable composite panels, are tightening legal regulations. In addition, existing halogen-based and heavy metal-based plastic flame-retardant cores generate a large amount of irritating fumes with high gas density during combustion, which increases the manufacturing cost of the composite panel due to the additional use of an anti-foaming agent and a depressant to compensate for this. The processing conditions are limited due to the generation of corrosive acids such as HBr and HCl during processing, and may cause more serious environmental problems when incinerated plastics are disposed of.

First, the problem with the conventionally proposed technique of imparting flame retardancy by using a halogen-based polymer will be described below;

 (1) Among the halogen flame retardants, the bromine flame retardant resin has the highest demand due to the generation of harmful gases such as dioxins, which has caused environmental pollution problems for a long time. It is known that there is a shortage of bromine-based flame retardant resins in each country. Albemarle of the United States introduced DBDPE (decabromodiphenylester) as a substitute for DBDPO (decabromodiphenyloxide), but it only reduces the toxicity of bromine compounds.

(2) As the eco-friendly flame retardant, the resin that satisfies the UL94 standard V-0 flame retardant by using phosphorus-based flame retardant has PC (polycarbonate) alloy, but this also applies to some specific materials because it has the disadvantage of deteriorating the physical properties of the polymer resin itself. .

(3) Japan's Mitsubishi Chemical produces its own flame-retardant resins, in which flame-retardant components are chemically bonded in plastic structures, but reactive flame-retardant cores containing vinyl and hydroxyl groups are expensive and complex in reaction processes. It takes a long time to manufacture.

Therefore, looking at the problems with the conventionally proposed and published patents or technologies that impart flame retardancy by using a non-halogen-based polymer for the purpose of solving the environmental problems as described above;

(1) US Pat. No. 3,314,322 uses a cyclic phosphorus (cyclic phosphorus) prepared by reacting a pentaerythrityl compound and a phosphorus compound as a flame retardant to increase the compatibility and flame retardancy of a polymer. There is this. However, this flame retardant is described in US Pat. No. 4,415,471, but there is a technique in which halogen organic compounds are used in parallel as a limitation of sole use of pentaerythrityl diphosphonate, which is a non-halogen-enhanced regulation. And problems against the technology.

(2) US Pat. No. 4,451,251, a technique in which diphosphonate and melamine pyrophosphonate are used together with poly (1,4-butylene terephthalate) polymer to impart good flame retardancy. The physical properties of cyclic phosphorus compounds are water-soluble or hydrolyzable, and thus have limitations in use. In addition, when the carbon number of the substituent R is 8 or more, there is a big problem in the impact strength and the tensile strength due to the sharply lower flame retardancy and low dispersibility.

(3) In US Patent No. 3915910, there is a technique of imparting flame retardancy by adding wood powder, aluminum hydroxide, magnesium hydroxide, etc. to polyolefin-based thermoplastic resins, but lacking flexibility due to the use of excess fillers, resulting in a complicated shape or a tube type composition. There are problems that are difficult to use.

(4) Resin composition technology in which aluminum hydroxide or magnesium hydroxide is added to phenol resin or melamine resin to impart flame retardancy described in European Patent No. 0899092 is added so that a small amount of thermosetting resin acts as a binder of an inorganic material, thereby providing flexibility. The lack of complex shapes or duvets is impossible. In addition, aluminum hydroxide is easily decomposed at about 200 ℃ has a problem that makes the extrusion processing difficult.

(5) Japanese Patent Publication No. 55-44890 describes a flame retardant resin composition prepared by adding borax and pearlite to a polyurethane resin, but borax is a substance regulated by the World Health Organization, and mixed with pearlite. It is uneconomical to require additional equipment.

(6) In addition, many domestic companies have made efforts to develop flame-retardant resins that do not use halogen materials, but the performance and environment are still inferior. As an example of non-halogen flame retardant research, domestic S and K have reported development of phosphorus-based flame retardant, but it is applied to specific models only due to performance problems, and plastic resin flame retardant technology is mainly used as additive type, content and mixing condition. As a result, there is a lack of research on a technology that satisfies both the flame retardancy and the mechanical properties of the composite panel. Therefore, Korean composite panel makers have to use expensive imported flame retardant cores when manufacturing plastic composite panels due to the flame retardant regulation policy of advanced countries. Currently, there is no special technology to manufacture eco-friendly flame retardant composite panels compared to developed countries.

Meanwhile, a flat composite panel such as a plastic core is made of a thermoplastic resin whose inner core is a polyolefin resin, and a composite panel manufactured by using the same has an excessive amount of flame retardant materials, especially inorganic materials, for the purpose of improving the thermally vulnerable problem. Although there are products with flame retardancy, the plastic core composite panel with flame retardancy is difficult to be molded into the inner core structure of the composite panel through the resin composition composed of inorganic materials to impart flame retardancy and to be applied continuously. It has been known to be difficult. Therefore, many composite panel manufacturing companies have been producing metal core composite panels for a long time. However, since the internal core is made of expensive non-ferrous metals such as aluminum and stainless steel, they are applied to only certain specific parts due to the high price. There are few commercialization cases due to the problems of non-environmental friendliness and the difficulty of applying a continuous process due to lack of flame retardancy and flexibility in manufacturing composite panels using plastic cores. With respect to the adhesive and production method of such a composite panel will be described below the domestic and foreign technologies and problems according to the conventionally proposed.

(1) As some aluminum composite panel manufacturers use thermosetting adhesive after manufacturing core by expansion and corrugation process of metal core, additional high temperature curing process is required or long time is required for room temperature curing. An on-site loading site will be required. As such, the metal core composite panel has a disadvantage in that the manufacturing process is complicated and the price is high, but the market is wide, but commercialization is not achieved universally.

(2) It is impossible to mass-produce by press-type lead welding on the inner core and metal plate adhesion, and the lead used for the adhesion is a harmful substance to human body, and has the technology of causing fatal obstacles,

(3) The high frequency etching technology of corona discharger has the problem of having the adhesive force and only need to finish the work for a limited time,

(4) In the process of bonding the core and the shell plate (B), a technique of manufacturing a composite panel by applying an adhesive to glass fibers instead of an adhesive film is used, the glass fibers absorbed a large amount of adhesive, and as a result a large amount Many patents have been registered and disclosed, such as an increase in the weight of the product according to the use of the adhesive and a technology having a disadvantage that is not beneficial to the environment or human body.

In addition, the technology that was found to be excellent in flame retardancy among the resin composition, in particular, the resin containing excess inorganic material is difficult to apply the continuous process is difficult to commercialize the composite panel.

Therefore, there are many technologies related to the flame retardant resin composition, but there are no patents and techniques related to the method of manufacturing a composite panel, in particular, a flame retardant core composite panel using the flame retardant resin composition.

The present invention has been made to solve the above problems,

In manufacturing a flame retardant core resin composition and a composite panel using the same, which does not contain heavy metals and halogens, the inner core is a polyolefin resin manufacturing process using a non-halogen-based and non-metal-based flame retardant and a flame retardant aid to form a resin composition;

Manufacturing a sheet-type flame retardant core through an extruder in a continuous process;

And it relates to an environmentally friendly flame-retardant resin composition and a method for producing a composite panel characterized in that it comprises a process for producing a composite panel.

In order to realize this, it provides a flame retardant resin composition for core that improves flame retardancy, mechanical properties, and processability by using a polyolefin resin, a flame retardant that does not contain heavy metals and halogens, an admixture, and an antioxidant, and thus disadvantages of conventional flame retardant plastics. The aim is to produce an eco-friendly flame retardant core resin composition that solves the problems that are harmful to the environment and human body.

In addition, thermoplastic regenerated resins belonging to the polyolefins used in the present invention have a problem inferior in molding processability, and therefore, it is known that it is difficult to obtain a molded article by injection or extrusion molding methods commonly used in general-purpose resins such as polyolefin resins. For this reason, the use of recycled resin is limited, and utilization of regeneration is not advanced. Moreover, since the recycled resin is a resin obtained by crushing the recovered sheet, fiber, or the like, it is usually irregular or flake, bulky, and has a poor transportation efficiency. Therefore, in consideration of the transport efficiency, it is expected that the recycled resin is pelletized. It is difficult to produce uniform pellets because of poor moldability. It is a reality that there is no method to satisfy the various problems of the above-described recycled resin.

Accordingly, another object of the present invention is to provide a recycled resin composition having improved moldability, such as injection moldability and extrusion processability, and a composite panel using the same.

And in the production of a flame retardant core composite panel using the composition of the flame-retardant resin composition for the purpose of the present invention, first to produce a flame-retardant sheet-like inner core through an extruder, and to manufacture a conventional composite panel somewhat in the present invention It is possible to manufacture the flame-retardant core composite panel continuously instead of intermittently, by significantly reducing the amount of adhesive required for bonding the metal plate and the inner core, thereby providing an environmentally improved product. The company aims to secure productivity and price competitiveness by reducing manufacturing costs such as labor costs and yield due to mass production of food products.

The composition of the present invention comprises (1) polyolefin resin, (2) flame retardant, (3) flame retardant, (4) lubricant, (5) antioxidant, polyolefin resin for preparing the composition of the present invention And a resin composition manufacturing process for quantitatively preparing flame retardants, flame retardant aids, lubricants, and antioxidants;

An internal core manufacturing process of putting the prepared resin composition into an extruder and manufacturing a core in a sheet form;

This is supplied to the hot roller (HR) in a lamination together with the metal sheet (B) and the hot melt adhesive sheet (C) and penetrates the hot roller (HR) while passing through the metal sheet (B) / adhesive layer (C) / inner core (A) / The composite panel which consists of a 5-layered structure of a contact bonding layer (C) / metal plate material (B) consists of a composite panel manufacturing process which manufactures continuously.

First as a material used in the composition of the present invention;

Resin used as the main component of the thermoplastic resin belonging to the polyolefin, polyethylene (PE, polyethtylene), polypropylene (PP, polypropylene), polycarbonate (PC, polycarbonate), acrylonitrile-butadiene-styrene resin (ABS, acrylonitrile butadiene), polybutylene terephtalate (PBT), polyethylene terephthalate (PET, polyethylene terephtalate), polyphenylene sulfone (PPS, polypenylene sufide), polystyrene (PS, poly styrene), vinyl chloride (PVC, polyvinyl chloride) and polyesterimide resins (PEI, polyetherimide) are used, and these resins are used as raw materials or recycled resins, either alone or by blending two or more materials.

Flame retardants used nitrogen-based melamine-based, phosphorus-based and inorganic-based flame retardants to solve the problem of toxic gases such as dioxins, highly toxic carcinogens, and furans during the combustion of existing flame retardant plastic composite panels. In particular, in the present invention, the selected nitrogen-based melamine phosphate (MP, melamine phoshphate) can be substituted if only one or more NH ₂ of the three NH ₂ of the melamine structure can be synthesized melamine derivatives of various substituents, but used in the present invention Nitrogen-based melamine phosphate reacts melamine and phosphoric acid with kaolin dissociation solution to make the flame retardant production temperature below 105 ℃, improves impact strength and tensile strength after processing with good dispersibility, as well as widely available non-halogen Flame retardants, and melamine polyphoshphate (MPP), non-halogen condensed phosphorus compounds for phosphorus, polyphosphate and red phosphorus, and inorganic hydroxides include aluminum hydroxide, magnesium hydroxide, Inorganic flame retardants such as zinc stannate and molybdate As the main raw material, there is no toxic gas emission during combustion and it is selected alone or two or more for the manufacture of resin compositions that satisfy the flame retardant standards of KS F 2271 flame retardant class 2 ~ 3, UL 94 standard V-0, V-1. Used.

The flame retardant auxiliary agent is used together in the resin composition containing the main flame retardant does not contain heavy metals and halogens to double the flame retardant effect, in the present invention used a phosphate ester compound. An an acid ester-based compound belongs to a flame retardant, but in the present invention was used to play a secondary role of the main flame retardant to double the flame retardant effect,

The lubricant is added to facilitate fluidity and releasability during the thermoforming of the thermoplastic resin. The activating action of glidants is closely related to the friction that occurs between objects. In the dynamic state of plastic molding, not only friction occurs between the polymer and the extruder but also friction between molecules. The generated frictional heat raises the temperature of the resin composition and finally decomposes the resin. Glidants were added to control these frictions. Therefore, the role of the lubricant added in the present invention forms the adsorption layer of the lubricant between the thermoplastic resin and the metal surface of the extruder, thereby reducing frictional heat and melting into the polymer or the melt to be located between molecular chains. Reduces friction and facilitates workability. That is, it prevents the deterioration of thermoplastic resin due to the shear stress between resins due to the reduced frictional heat and reduces the pressure exerted on the back of the extruder by the extrusion screw. It improves productivity by shortening. Therefore, by using fatty acids as a lubricant, it also serves to improve the miscibility of different substances added to the thermoplastic resin to prevent mechanical property degradation.

Antioxidants were added for the purpose of inhibiting and preventing plastics made of thermoplastic resins from oxidatively deteriorating by oxygen in the air and causing deterioration in production and use. Degradation reaction by plastic oxidation is radical reaction and is made by different chemical reaction such as chain growth and peroxide decomposition. Accordingly, in the present invention, in order to suppress and prevent the oxidative degradation reaction, in the suppression of the chain start reaction, the suppression of the chain growth reaction, and the suppression of decomposition of the peroxide, the present invention captures the generated radicals and prevents the progress of the radical chain reaction. The primary antioxidant was added, and the secondary antioxidant, which is a peroxide decomposer, having the effect of decomposing into a radical-free form was added together. As the primary antioxidant described above, phenol-based antioxidants, monophenol-based, bisphenol-based and polymer-type phenol-based antioxidants were used, and sulfur-based antioxidants were used as secondary antioxidants to induce molecular chain cleavage by introducing peroxides. Antioxidants and phosphorus antioxidants were used. In addition, a resin composition composed of ABS resin, which is a resin easily oxidized depending on the thermoplastic resin, was used in combination of two or more antioxidants.

The amount of the polyolefin-based thermoplastic resin is preferably 35 to 64% by weight based on the total weight of the resin composition, if less than 35% by weight, the workability is poor to maintain mechanical properties, making it difficult to manufacture a molded article, 64 If the weight percentage exceeds, there is a problem that the flame retardancy of the resin composition is sharply lowered due to the flammability of the polyolefin-based thermoplastic resin.

In addition, the molding processability of the recycled resin used in the present invention has no difficulty in manufacturing a molded article, especially a core, by injection or extrusion molding due to compatibility and modification of materials used in the composition of the present invention with thermoplastic resins. . Above all, the lubricant in the composition was compatible with the flame retardant resin composition of the present invention and could be used without particular limitation.

In the above flame retardant was used 30 to 55% by weight, flame retardant auxiliary agent 5 to 10% by weight, 0.01-6% by weight of lubricant, 0.01-0.6% by weight of primary and secondary antioxidants were used.

Melt polyethylene (PE) in various polyolefin thermoplastic resins, MP (melamine phoshphate) in flame retardants, phosphate ester compound as flame retardant, stearic acid as lubricant, Irganox 1010 as primary antioxidant, Irgafos 168 as secondary flame retardant, through extruder The mixture was kneaded to prepare a blended resin composition sought in the present invention. It is a step before the extruder is manufactured to produce pellets for easy use and improvement of workplace environment.It is thermoplastic resin, MP (melamine phoshphate) as flame retardant, phosphate ester compound as flame retardant, stearic acid as lubricant, and primary antioxidant Irganox. 1010, the secondary antioxidant Irgafos 168 is melt-kneaded in a Banbury mix, and then made into a resin composition manufacturing process step of extrusion molding into pellet resin. At this time, the extrusion temperature conditions are preferably 160 ~ 200 ℃, the extruder equipment used in the resin composition production in the present invention is shown in [1] and [2].

And lubricants, preferably up to 6% by weight. When using more than 6% by weight of the lubricant stearic acid, rather than reducing the flame retardancy, forming a surface on the flame retardant core surface due to the weakening of the adhesion between the inner core (C) and the metal plate (B) of the five-layer structure There was a problem that the panel manufacturing becomes difficult.

The resin composition pellets prepared by the above process is the next step, the sheet-shaped core manufacturing process, the continuous core manufacturing equipment developed for the present invention, that is, in the manufacture of a wide sheet-shaped inner core through T-Die In the manufacture of sheet-type cores with no adhesive applied on both sides, or when manufacturing sheet-type cores, the adhesive is applied to the outer surface of the sheet-shaped inner core by coextrusion, and the inner surface is manufactured by applying the adhesive to the outer surface. The core has the effect of improving and simplifying the process line of the adhesive layer (C) in the composite panel manufacturing schematic shown in FIG. 3, and thus, the composite panel can be manufactured while passing the hot roller (HR) by supplying only the metal plate (B). In the final line, it is possible to manufacture a composite panel continuously by attaching a cutting (D) device that is cut to a desired size.

In addition, in the case of the inner core manufactured by applying the adhesive to the outer surface by the co-extrusion method described above, to prepare a special purpose product to be inserted for improving the physical properties of the composite panel, that is, the reinforcement (shown in Figure 3) ( E) has the advantage of easy adhesion with the inner core.

The inner core (A) manufactured as described above is supplied to the hot roller (HR) in a lamination together with the metal sheet (B) and the hot melt adhesive layer (C) to penetrate through the hot roller (HR), and the metal sheet (B) / adhesive layer A five-layered composite panel composed of (C) / inner core (A) / adhesive layer (C) / metal plate (B) layer is continuously manufactured.

At this time, the metal plate (B) was used alone or alloy composed of two or more components composed mainly of aluminum (Al), zinc (Zn), titanium (Ti).

The flame retardancy test for the resin composition prepared in the above process was 5mm × 5mm in size of the test piece, and it was shown in Table 1 by evaluating the self-extinguishing property using the vertical method. The flame retardant used in the present invention for the flame retardancy test for the prepared resin composition was flame retardant from 30% by weight of the total amount of the flame retardant compared to the total content, the conventional halogen-based flame retardant resin using only V-0 grade Although the flame retardancy was expressed, there was a disadvantage in that an unfavorable smell peculiar to Br compound was generated. In the resin composition of the present invention, there was no dripping phenomenon, but a resin using a halogen flame retardant produced a dripping phenomenon. As a result of this, Figure 4 shows the state after the flame-retardant test of the halogen-based flame retardant core material and the resin composition core material of the present invention. It was found that the resin composition formulated in the present invention was even better than the core material using the halogen flame retardant.

Item Specimen Specification T ₁ (seconds) T ₂ (seconds) Judgment Halogen
Flame retardant 40 5 × 5 ㎜ One One V-O 30 One One 20 One 1-2 Suzy
Composition 60 One One V-O 40 One One 30 One 1-2

[Flame Retardant Test]

◎ Related Standards: UL (underwriters laboratories) 94.

◎ Heat source: Use methyl alcohol lamp.

◎ Firework length: 5cm, Reaching length: 1cm

◎ Heating method:

― 10 seconds heat up / off time check: T ₁ .

― 10 seconds heat up / off time check: T ₂ .

There may be a plurality of embodiments of the present invention, hereinafter, the most preferred embodiments will be described in detail. Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.

Therefore, examples and working examples of the resin composition and its composite panel prepared while varying the content and amount of polyethylene (PE) resin among various polyolefin thermoplastic resins will be described.

Example 1

40% by weight of polyethylene (PE), 50% by weight of MP (melamine phoshphate) in flame retardant, 7% by weight of phosphate ester compound as flame retardant, 2.85% by weight of stearic acid as lubricant, 0.05% by weight of primary antioxidant Irganox 1010, secondary 0.1 wt% of the antioxidant Irgafos 168 was melt kneaded through an extruder to prepare a resin composition. A composite panel, in particular an aluminum composite panel, was prepared using the composite panel manufacturing apparatus with the resin composition.

Comparative Example 1

In Example 1, in the case of flame-retardant composition using aluminum hydroxide instead of MP (melamine phoshphate) in the flame retardant, without using a lubricant, 35% by weight of polyethylene (PE), 50% by weight of aluminum hydroxide as an inorganic flame retardant , 11% by weight of the phosphate ester compound, 1.5% by weight of the primary antioxidant Irganox 1010, 2.5% by weight of the secondary antioxidant Irgafos 168 as a flame retardant adjuvant, uniformly blend blended in an extruder, and then pelletized.

Comparative Example 2

For surface test and gas hazard test according to KS F2271 standard, 60% by weight of polyethylene (PE) and 40% of MP (melamine phoshphate) were compounded to prepare a resin composition, and a flame retardant core (220mm × 220mm) was prepared through the prepared resin composition. X 3.5 mm) was prepared. Then, both sides of the flat plate and the 0.5mm aluminum flat plate (B) were attached to the hot melt contact sheet (C), and then thermally compressed to prepare an aluminum composite panel having a total thickness of 4mm.

Hereinafter, with reference to the accompanying drawings will be described in detail a resin composition and a preferred embodiment using the same.

Experimental Example 1

Flame retardancy test results described above for the resin compositions formulated in Example 1 and Comparative Example 1. Flame retardancy was shown that Comparative Example 1 is superior to Example 1 while the flexibility is greatly reduced. However, in the case of the resin composition described in the present invention, it was possible to manufacture cores continuously. The particle size of the added inorganic flame retardant could be selectively used in various ways by the manufacturing process. However, when the particle size was selectively used at 20 μm or less, good impact strength and moldability were exhibited.

Experimental Example 2

The surface test and gas hazard analysis of one side of the manufactured composite panel by heating 1.5 KW electric heater as the main heat source and propane gas as the sub heat source for 350cc / min for 6 minutes are shown in [Table 2] and [Table 5], respectively. It was.

As shown in Table 2, the surface test was performed;

The number of test specimens was three, and the size of the test specimens was 220 mm in width and length, respectively, and the thickness was 4 mm, which is the thickness of a conventional composite panel product. The specimen was left in a well-ventilated place for about one month after manufacture, dried in a dryer at 35-45 ° C. for 24 hours, and then used in the desiccator for 48 hours. In the furnace for the surface test of the test body, the main heat source is, in principle, an electric heat with a constant voltage device, and the sub-heat source is, in principle, propane gas. It was further heated for 3 minutes with the main heat source. The heating test was started after the display temperature of the thermocouple measuring the exhaust temperature had dropped to about 50 ° C.

First, after the test, the weight loss of the resin composition of the present invention was 2.1g, 2.2g, 1.9g in the weight loss section of the test specimen, respectively, and the exhaust temperature curve of the heating furnace was a solid-line recording tube. Measurements were made with an automatic equilibrium recording thermometer and shown in FIGS. 5, 6, and 7, respectively. When heated for 10 minutes, the exhaust temperature shown in the following [Table 3] was performed within an error range within 20 ℃. In order to measure the coefficient of smoke per unit area, a rectangular collecting box (inner size shall be 1m in height and 1.41m in the other two sides) shall be provided with smoke stirrer and light quantity measuring device. The photometric device sucked smoke at a flow rate of about 1.5 liters per minute at a position 30 cm below the ceiling surface in the center of the collecting box. The measurement of the amount of light passing through the smoke was performed every 15 seconds during the heating test.

The area of the part where the exhaust temperature curve exceeds the standard temperature curve and the area surrounded by the standard temperature curve (unit: ℃ × min, hereinafter referred to as the temperature time area) is the standard temperature of the test specimen. As a relative value, the heat generation degree of the material was expressed as 0. Therefore, it can be seen that it has excellent flame retardancy because it does not exceed 350, the criterion for determining the flame retardant material.

And the coefficient of smoke per unit area (C _A ) is a coefficient measuring the degree of reduction of light transmission by the light quantity device by collecting the smoke generated from the heating furnace from the collecting box,

Fume coefficient (C _A ),

In this formula, I _o and I are

I _o : Light intensity at the start of the heating test (unit ㏓)

I: The minimum intensity of light in units of heat test.

Therefore, in Table 2 shown below, the flame retardant class 1 criterion is 30 or less, the flame retardant class 2 criterion is 60 or less, the flame retardant class 3 criterion is 120 or less, and the resin composition of the present invention is measured at 2.0. I belonged to the first class flame retardant.

Afterflaming is a phenomenon that the flame remains on the test body even after the burner and the heating wire are turned off after the end of the test, which is 0 seconds.

In addition, the crack width on the back side of the test specimen was 0 mm, and no melting or deformation occurred.

Table 4 shows the criteria for determining the flame retardant water supply.

Exam name Surface test Specimen division Example 1 Comparative Example 1 Comparative Example 2 Size (mm2) 220 × 220 220 × 220 220 × 220 Thickness (mm) 4.0 4.0 4.0 Weight (g) 292.1 299.3 261.8 Weight loss after test (g) 2.1 2.2 1.9 Exhaust Temperature Curve See Figure 5 See Figure 6 See Figure 7 Exhaust temperature and smoke Temperature time area
(℃ × min) Within 3 minutes radish radish radish 3 minutes later 0 0 0 Per unit area
Coefficient of Smoke (C _A ) 2.0 2.0 2.0 Afterglow time 0 0 0 Melting over the entire thickness
(Full melting of core material in case of composite structure) none none none  crack width of m surface (mm) 0 0 0 Harmful deformations on fire none none none

[Surface Test]

◎ Related Standards: KS F 2271.

◎ Test method: After heating with the subheat source on the specimen of 220mm width and 220mm length, it is continuously heated for 6 minutes by the main heat source and the sub-heat source, and the loss, temperature time area and smoke coefficient per unit area, residual flame, melting, crack, deformation Measure.

◎ Criteria:

― Loss: Less

— Temperature time area: shall not exceed the standard temperature curve within 3 minutes of the start of the test;

-Coefficient of smoke per unit area: 350 or less.

Afterglow time: less than 30 seconds.

-No melting, cracking (less than 1/10 of thickness), no deformation.

Elapsed time (min) One 2 3 4 5 6 7 8 9 10 Specific air temperature (℃) 70 80 90 155 205 235 260 270 290 305

Metric Flame retardant class 1 Flame retardant class 2 Flame retardant class 3 Exhaust temperature Standard temperature
Should not exceed Standard temperature within 3 minutes
Must not exceed Standard temperature within 3 minutes
Must not exceed Temperature time area 0 100 or less 350 or less Smoke coefficient 30 60 120 Afterglow After heating
Must be no longer than 30 seconds After heating
Must be no longer than 30 seconds After heating
Must be no longer than 30 seconds Melting No melting No melting No melting crack Crack width on the back of the specimen is less than 1/10 of the total thickness Crack width on the back of the specimen is less than 1/10 of the total thickness Crack width on the back of the specimen is less than 1/10 of the total thickness Specimen deformation No deformation No deformation No deformation

Gas hazard tests are as shown in Table 5, the test piece, and the number is two, and the size of the test specimen, and a vertically and horizontally 220mm, also the thickness was set to 4mm in size. The heat source of the furnace was the same as the surface test, but when heated for 6 minutes, the exhaust temperature shown in [Table 6] was performed within an error range within 10 ℃. The air is supplied only during heating, and the supply amount is 3.0 liters per minute by the primary feeder of the furnace and 25.0 liters per minute by the secondary feeder. The gas is discharged only during heating, and the discharge is 10.0 per minute. L was set. At the start of the heating test, the temperature in the test box shall be about 26 to 28 ° C, and a rotating basket containing one experimental mouse (ICR female, 5 weeks old and weighing 20 to 21g), one by one (rotating part of the rotating basket) Is made of aluminum in principle, and its weight is less than about 75g.) 8 pieces are put in the test box. The measurement of the time from the start of the heating until the experimental mice stop the behavior (hereinafter referred to as the behavior stop time) was equipped with an automatic recording device. Therefore, after the test body was put in a heating furnace for 6 minutes (propane 3 minutes, heating wire 3 minutes) and heated, the combustion gas from the test body went through the stirring box to the rotating basket box and observed the effect on the experimental mice.

The behavioral stop time of the test mice after heating was recorded for each experimental mouse for 15 minutes after the start of heating, and if the average behavioral stop time is greater than 9 minutes, it is a criterion of compliance. As a result of the excellent flame retardancy of the present invention, it was confirmed that the toxic gas emission was reduced, thereby eliminating the harmful effects of the human body due to the effect of reducing the suffocation effect caused by the toxic gas. Therefore, it is suitable for the surface test and the gas hazard test. It turned out.

Exam name Gas Hazard Test Test body division Example 1 Comparative Example 1 size() 220 × 220 220 × 220 Thickness (mm) 4.0 4.0 Weight (g) 302.0 314.7 Weight loss after test (g) 2.5 2.3 mouse Pedigree and Gender ICR, female ICR, female Average weight (g) 20.2 20.6 Test box temperature (℃) Early 26.3 27.3 Best 32.7 32.6 Mouse average behavior stop time 15 minutes 00 seconds 15 minutes 00 seconds Standard Deviation 00 minutes 00 seconds 00 minutes 00 seconds Mouse pause time 15 minutes 00 seconds 15 minutes 00 seconds

[Gas Hazard Test]

◎ Related Standards: KS F 2271.

◎ Test Method: Measure the average time to stop the behavior of eight ICR (Institute of Cancer Research) female mice in the smoke generated by heating specimens 220 mm wide and 220 mm long.

◎ Judgment criteria: The average stop time is 9 minutes or more.

Elapsed time
(min) One 2 3 4 5 6 Exhaust temperature
(℃) 70 85 100 140 170 195

[Table 7] shows the results of measuring the sound insulating properties, flexural strength, elongation, tensile strength, adhesive peeling strength, and appearance properties of the composite panel after the composite panel was manufactured using the flame retardant core prepared through the flame retardant resin composition. More than 90% lighter than the inner core of general composite panel, flame retardant and gaseous hazard are flame retardant grades 2 ~ 3 and mouse behavior stop time, which is environmental evaluation of flame retardant core, is 15 minutes and 00 seconds. The result was better than 99% (28.5dB) of sound insulation, 137.6N / mm ² and 196N / 25mm, which are better than 130N / mm ² and 147N / 25mm, which are standard in flexural strength and peel adhesion strength. It was obtained, and also excellent in the flatness without the appearance distortion, pollution resistance, and temperature repeatability. FIG. 8 is a measurement of sound insulation at several different acoustic frequencies, and it can be seen that the sound insulation performance becomes better as the frequency increases.

Evaluation item standard Test result Evaluation standard Sound insulation (dB) 20-28 / 500 MHz 28.5 KS F 2802 Flexural Strength (N / mm ² ) > 130 137.6 KS F 4737 Thin adhesive strength (N / 25mm) > 147 196.0 KS F 4737 Adhesion 100/100 100/100 KS F 4737 Pollution resistance Standard Gray 5 Standard Gray 5 KS F 4737 Cold and hot repeatability No abnormality clear KS F 4737

Looking at the substantial effect on the specific action of the present invention;

Nitrogen-based melamine phosphate used in the present invention is a white powder prepared by reacting melamine and phosphoric acid in a kaolin dissociation solution. In addition, the flame retardancy of the substituted melamine phosphate itself was excellent, but even when used with other flame retardants, it showed excellent flame retardancy.

Flame retardant supplements have been used to replace some or all of the flame retardants so that they have an economic effect that can bring about cost-effectiveness and functional improvement at the same time.

In addition, the antioxidant for plastics used in the present invention stabilizes radicals by reacting with radicals generated by the oxidation of polyethylene (PE), and thus, Irganox 1010, polyethylene (PE) as a primary antioxidant to stop the chain oxidation reaction caused by radicals. Irgafos 168 was used to change the unstable peroxide produced by the oxidation of to a stable material to inhibit the occurrence of further oxidation. It was non-toxic and had good compatibility with resins without disturbing stability, activity and other resin processability at processing temperatures. In addition, it did not cause a chemical reaction with other additives, it was found to exhibit good mechanical properties as shown in [Table 7] good mixing properties with resin powder, pellets and the like.

Therefore, the manufacturing method of the composite panel according to the present invention was found to be able to significantly improve the physical properties and quality of the product than the existing method.

In addition, the present invention can be modified and implemented in various ways without departing from the technical gist of the present invention without departing from the embodiments. In the present invention, a resin produced using polyethylene (PE) resin Although a specific product such as a flame retardant polygonal core composite panel using a composition has been described as an example, its application range is of course wide because it can be applied to composite panels made of other resins.

As described above, the present invention provides a composite panel made of a flame-retardant resin composition that can reduce such damage in preparation for the tendency of damage caused by asphyxiation by toxic gas rather than direct damage by fire. Economic practicalization was also developed in consideration.

Therefore, the flame retardancy and eco-friendliness of the product itself, and the inner core of the sheet-type manufactured by the resin composition of the present invention, as a substitute for the existing highly toxic halogen-based and heavy metal-based flame retardant materials, are manufactured by employing pneumatic methods. Special production is made according to the preferences, and it is accompanied by environmental friendliness and human benefits. Finally, the manufactured composite panel has many advantages that the product competitiveness is superior due to easy mass production.

Claims (4)

(a) consisting of polyethylene, polypropylene, polycarbonate, acrylonitrile-butadiene-sutyrene resin, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfone, polystyrene, polyvinyl chloride, polyesterimide and mixtures thereof 35 to 64% by weight of the thermoplastic polyolefin resin selected from the group, (b) 30 to 55% by weight of a flame retardant selected from the group consisting of melamine flame retardants, phosphorus flame retardants, inorganic flame retardants and mixtures thereof; (c) 5 to 10 weight percent of flame retardant adjuvant which is a phosphate ester compound, (d) 0.01 to 6 weight percent of a lubricant which is stearic acid and (e) 0.01 to 0.6% by weight of a secondary antioxidant selected from the group consisting of primary antioxidants, which are phenolic antioxidants, sulfur-based antioxidants, phosphorus antioxidants and mixtures thereof Flame-retardant core resin composition containing. The method of claim 1, wherein the polyethylene, polypropylene, polycarbonate, acrylonitrile-butadiene-sutyrene resin, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfone, polystyrene, polyvinyl chloride and polyesterimide A flame retardant core resin composition, which is a recycled resin. The flame retardant core resin composition of claim 1, wherein the melamine-based flame retardant is a melamine phosphate prepared by reacting melamine and phosphoric acid in a kaolin dissociation solution under a temperature condition of 105 ° C. or less. delete

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