WO2010008182A2 - Composition for an incombustible aluminum composite panel core - Google Patents

Abstract

The present invention relates to a composition for a flame-retardant aluminum composite panel core wherein the composition is prepared by mixing a non-halogen-based flame retardant and a foaming agent to polyolefin, compounding the mixture by using a kneader or a Banbury mixer, and foaming the compound in an extrusion process using a sheet molding machine to lower the specific gravity of the composition to 1.35 or less. The composition for an aluminum composite panel core prepared according to the present invention is lightweight and exhibits excellent flame retardance, extrusion workability, and bending properties.

Description

Nonflammable Aluminum Composite Panel Core Composition

The present invention relates to a composite composition for an aluminum composite panel core material, and more specifically, a thermoplastic polyolefin is mixed with a non-halogen-based flame retardant and a thermally expandable microcapsule, which is a foaming agent, to prepare flame retardant class 2 and flame retardant class 3 of [KS F4737 aluminum composite panel]. The present invention relates to a non-combustible polyolefin composition characterized by lowering the specific gravity of an aluminum composite panel core material to 1.35 or less by foaming thermally expandable microcapsules.

Aluminum composite panels used in building materials and exterior materials have a multilayer structure in which aluminum, an adhesive layer, a core material (non-flammable resin composition), an adhesive layer, and aluminum are sequentially formed, and the multilayer structure is thin to reduce the use of expensive aluminum discs. After having an aluminum plate which has aluminum thickness, preferably 0.5 mm or less, it has a structure which adhere | attaches a nonflammable polyolefin resin composition to the said aluminum plate as a core material.

However, the non-flammable resin composition generally has a high specific gravity by using a large amount of flame retardant, as well as a problem that the extrusion processability is significantly lowered by using a compatibilizer to improve physical properties.

For example, Korean Patent Publication Nos. 2002-0049444 and 2002-0036291 disclose nonflammable polyolefin resin compositions comprising 15 to 25% by weight of low density polyethylene, 65 to 80% by weight of magnesium hydroxide and 5 to 10% by weight of a compatibilizer, and The manufacturing method of the used aluminum composite panel is disclosed.

In addition, the Korean Patent Registration No. 10-0680822 shows an example of using a lightweight filler in place of a compatibilizer for the problem of extrusion processing and material weight. However, due to the excessive particle size and hardness of the lightweight filler, the extruder screw ( Another problem that the wear problem of the screw) and the resulting extrusion amount is non-uniform was produced.

In order to overcome the above-mentioned problems, the present inventors have continuously studied the non-combustible thermoplastic polyolefin composition and use a blowing agent [Matsumoto Yushi-Seiyaku Co., Ltd., F-190D] to dramatically increase the specific gravity compared to the conventional composition. A flame retardant grade 2 or higher product was prepared according to KS F2271 (a method for testing flame retardancy of embedded materials and structures of buildings) which was lowered and solved the extruder wear problem fundamentally and can be easily extruded in a conventional extruder.

The present invention is to solve the drawbacks of the conventional non-combustible resin composition, that is, not only high specific gravity using a large amount of flame retardant, but also a problem that the extrusion processability is significantly reduced by using a compatibilizer to improve physical properties, In addition, the second problem is to solve the problem of wear of the extruder screw (Screw) and the resulting non-uniformity of the extrusion amount, which is a problem when using a lightweight filler instead of a compatibilizer.

The present invention is 15 to 35% by weight thermoplastic polyolefin to solve the above problems; 60 to 80% by weight of non-halogen flame retardant; Thermally expandable microcapsules as blowing agents; The flame retardant polyolefin resin composition, which is composed of 0.1 to 5.0% by weight and is characterized by lowering the specific gravity of the aluminum composite panel core to 1.35 or less, is an important means for solving the problem.

In addition, the present invention is a non-halogen flame retardant selected from magnesium hydroxide, aluminum hydroxide, magnesium carbonate, melamine cyanurate (MC), red, ammonium polyphosphate (APP), melamine phosphate (MP), melamine polyphosphate (MPP) Or to solve the above problems by providing a flame retardant polyolefin resin composition for aluminum composite panel core, characterized in that more than two.

Meanwhile, the thermally expandable microcapsules, which are used in the present invention, have a structure in which a liquid low boiling hydrocarbon is wrapped with a thermoplastic shell, and when heated, the shell of the polymer softens and the liquid hydrocarbon inside changes into a gas. The capsule expands 50 ~ 100 times under the pressure to form hollow particles. The hydrocarbon used for foaming is trapped inside the shell, so it can be introduced into the cell. It not only prevents serious damage to flame retardancy, but also provides a characteristic that can significantly lower the specific gravity.

The thermoplastic polyolefin composition of the present invention significantly reduced specific gravity compared to conventional materials by sufficiently impregnating a high content of a non-halogen flame retardant and a foaming agent (thermally expandable microcapsules) in a polyolefin resin and then foaming it in a closed cell form in an extrusion process. As a result, the degradation of the flame retardant (or flame retardant) performance that occurs in the open cell does not occur. In addition, the elasticity of the thermally expandable microcapsules not only has excellent bending properties, but also prevents wear of the extruder screw, which has occurred in existing lightweight materials.

In addition, stable results can be obtained for nonflammable and gaseous hazardous experiments according to KS F2271.

BRIEF DESCRIPTION OF THE DRAWINGS The figure which shows the cross section of the flame-retardant resin composition manufactured by this invention.

The present invention relates to a non-flammable polyolefin composition comprising heat-expandable microcapsules [Matsumoto Yushi-Seiyaku Co., Ltd., F-190D] as a non-halogen-based flame retardant and a blowing agent in thermoplastic polyolefin. Provided is a thermoplastic polyolefin composition having a specific gravity of 1.35 or less and satisfying flame retardant secondary and flame retardant tertiary standards of [KS F4737 aluminum composite panel].

As the thermoplastic polyolefin used in the present invention, a thermoplastic resin, a thermoplastic rubber, a thermoplastic elastomer alone or a mixture of two or more thereof is suitable, and the usable thermoplastic resin is 160 in a differential scanning calorimetry (DSC) measurement according to ASTM D 3417. A Tm value of less than or equal to, preferably less than or equal to 140 ° C, for example polyethylene (PE), polypropylene (PP), polybutene (PB-1), ethylene-propylene copolymer (EPR), propylene alpha olefin air Copolymer (trade name: Versify), ethylene-butene copolymer (trade name: Tafmer), ethylene-hexene copolymer, ethylene-octene copolymer, ethylene vinyl acetate (EVA), ethylene ethyl acrylate (EEA), ethylene methyl acrylate ( EMA), or modified (acrylic acid or maleic anhydride) resins thereof. In addition, the usable thermoplastic rubbers and thermoplastic elastomers may have a density of 0.840 g / cm 3 to 0.930 g / cm 3 in the density measurement of ASTM D 1505. Examples thereof include SBS (Styrene-Butadiene-Styrene copolymer) and SIS. (Styrene-Isoprene-Styrene copolymer) and their hydrogenated products, SEBS (Styrene-Ethylene-Butylene-Styrene copolymer), SEPS (Styrene-Ethylene-Propylene-Styrene copolymer) and HSBR (Hydrogenated Styrene-Butadiene Rubber), The amount of thermoplastic polyolefin used in the dynamic crosslinking of ethylene-propylene-diene monomer (EPDM) / polyolefin resin or modified (such as acrylic acid or maleic anhydride) is preferably 25 to 35% by weight in the total compound composition. .

The non-halogen flame retardant according to the present invention is used at 60 to 80% by weight, preferably 70 to 75% by weight relative to the total composition, and any flame retardant that can be used as long as it is commonly known to those skilled in the art may be used. Preferably, magnesium hydroxide, aluminum hydroxide and magnesium carbonate, melamine cyanurate (MC), melamine phosphate (MP), melamine polyphosphate (MPP), ammonium polyphosphate (APP), red, zinc borate, etc. It can be used, the preferred particle size is 1 to 70㎛, specific surface area (BET) 0.4 to 35 m 2 / g is good.

Here, if the content of the non-halogen flame retardant is 60% by weight or less, the flame retardancy is reduced, for example, flame retardant grade 2 or less based on KS F2271, if the content is higher than 80% by weight, the workability due to the increase in extrusion load It becomes difficult and it is difficult to manufacture an optimum object.

The foaming agent according to the present invention is included in the resin composition to reduce the specific gravity of the resin composition. Any foaming agent may be used as long as it is used for this purpose, but it is preferable to form a closed cell.

This is because when the open cell is formed, not only the nonflammability (or flame retardancy) is rapidly damaged due to the oxygen inside the open cell, but also the adhesive strength with the aluminum plate is lowered.

Therefore, as the blowing agent according to the present invention, thermally expandable microcapsules containing low-boiling hydrocarbons are effective, and in particular, it is preferable to maintain an initial decomposition temperature of at least 150 ° C and a maximum degree of foaming at 210 ° C to 240 ° C. 0.1 to 5% by weight or less, preferably 1 to 3% by weight relative to the total resin composition.

When the content of the blowing agent is added in more than 5% by weight relative to the total weight of the resin composition, not only the flame retardancy is lowered but also the problem that the strength of the core material is weakened and brittle may occur.

In addition, the thermally expandable microcapsules used in the present invention [Matsumoto Yushi-Seiyaku Co., Ltd., F-190D] does not cause the wear problem of the screw when forming the sheet (SHEET) due to the elasticity of the shell material and flexible to the foam It also has a feature of providing (bending property).

On the other hand, the non-halogen-based non-flammable polyolefin composition according to the present invention is a compatibilizer, antioxidant, processing aid, inorganic filler (Mica, fly ash, graphite powder, calcium carbonate, talc, etc.), filler dispersant and / or dehumidifying agent in addition to the above components , Colorants and the like can be further added in small amounts.

The manufacturing method of the nonflammable polyolefin composition of this invention is as follows.

First, 15 to 35% by weight of thermoplastic polyolefin, 60 to 80% by weight of non-halogen flame retardant, 0.1 to 5.0% by weight of blowing agent [Matsumoto Yushi-Seiyaku Co., Ltd., F-190D] and thermal stabilizer 0.2% by weight of the mixture of the antioxidant and the Kneader or Banbury mixer was melt-dispersed at 150 ℃ or less, and then passed through a single screw extruder of 140 to 150 ℃ to prepare a non-halogen-based non-flammable polyolefin resin composition on the pellet. The thermoplastic polyolefin composition thus prepared has a specific gravity of about 1.3 to 1.7 since the blowing agent is not decomposed, but the specific gravity after processing through a sheet extruder has a value of about 0.4 to 1.5 depending on the content of the blowing agent. do.

It is very important to give the foam a suitable density, in order to increase the adhesive strength with the aluminum sheet. That is, if the ratio of the thermally expandable microcapsules in the foam is too high, the foam is not dense and brittle, and the adhesive strength with the aluminum sheet is low, which is not suitable for core materials. As a result of observing the cross section of the foam with a scanning electron microscope (SEM), in order to have a suitable density as a core material, the ratio of thermally expandable microcapsules in the cross section of the foam is 10% to 80%, preferably 20% to 75%, more preferably. Preferably from 40% to 65%. If the ratio of the thermally expandable microcapsules is less than 10%, it is difficult to expect economic feasibility. If the ratio of the thermally expandable microcapsules is 80% or more, the foam strength is low, and the foam collapses when measuring the adhesive strength with the aluminum sheet.

The relationship between the ratio and the density of thermally expandable microcapsules in the cross section of the core material is as shown in the following table.

Table 1: Relation between the ratio and the density of thermally expandable microcapsules in the cross section of the core material

Table 1

division	(One)	(2)	(3)	(4)	(5)
Density (ρ)	1.003	0.875	0.818	0.759	0.702
Ratio (A / S)	~ 40	To 50	To 65	To 70	To 75

                                 ※ S is the foam cross section, A is the foam cross section

Test method of this product is as known in the existing patent (Korean Patent Publication No. 2002-0049444) and will be described in more detail the present invention through the following examples, the following examples are for the purpose of explanation of the present invention It is not intended to limit this.

Example 1

20.30% by weight of a mixture of low density polyethylene (Hanhwa Petrochemical, LDPE 737, Tm = 103 ° C) and ethylene vinyl acetate (Hanhwa Petrochemical, EVA 1125, Tm = 80 ° C), 70.00% magnesium hydroxide, 5.00% calcium oxide, dispersant 3.00 Weight%, foaming agent [F-190D, Matsumoto Yushi-Seiyaku Co., Ltd.] in a kneader (75L) at 140 ℃ with 0.20% by weight of a mixture of antioxidant and heat stabilizer, melt kneaded, and then uniaxially Prepared on pellet through an extruder.

Example 2

19.30% by weight of a mixture of low density polyethylene (Hanhwa Petrochemical, LDPE 737, Tm = 103 ° C) and ethylene vinyl acetate (Hanhwa Petrochemical, EVA 1125, Tm = 80 ° C), 70.00% magnesium hydroxide, 5.00% calcium oxide, dispersant 3.00 Wt%, 2.50 wt% of blowing agent [F-190D, Matsumoto Yushi-Seiyaku Co., Ltd.] together with 0.20 wt% of a mixture of antioxidant and heat stabilizer in a kneader (75L) at 140 ° C. Prepared on pellet through an extruder.

Example 3

21.70% by weight of ethylene vinyl acetate (Hanhwa Petrochemical, EVA 1159, Tm = 71 ° C), 70.00% by weight of melamine cyanurate, 5.00% by weight of dispersant, blowing agent [F-190D, Matsumoto Yushi-Seiyaku Co., Ltd 3.00 wt% was mixed with 0.30 wt% of a mixture of antioxidant and heat stabilizer in a kneader (75L) at 125 ° C., and kneaded and prepared into pellets through a single screw extruder.

Example 4

20.30% by weight of a mixture of polybutene (PB-1, Tm = 135 ° C., MI = 27.5) and a propylene-α-olefin copolymer (Dow, Versify 2300, Density = 0.867 g / cm3) and magnesium hydroxide 70.00% by weight, oxidation 5.00% by weight of calcium, 3.00% by weight of dispersant, and 1.50% by weight of blowing agent [F-190D, Matsumoto Yushi-Seiyaku Co., Ltd.] were added to kneader (75L) at 150 ° C with 0.20% by weight of a mixture of antioxidant and heat stabilizer. After melting and kneading, it was prepared into pellets through a single screw extruder.

Example 5

20.80% by weight of a mixture of polypropylene (Korean emulsifier, 8088, Tm = 136 ° C) and styrene thermoplastic rubber (Kuraray, Hybra 7311, Density = 0.89g / cm3), 70.00% by weight of magnesium hydroxide, 5.00% by weight of calcium oxide, dispersant 3.00% by weight, 1.00% by weight of the blowing agent [F-190D, Matsumoto Yushi-Seiyaku Co., Ltd.] was mixed with 0.20% by weight of a mixture of an antioxidant and a heat stabilizer in a kneader (75L) at 150 ° C., followed by melt kneading. Prepared into pellets via a single screw extruder.

Example 6

16.80% by weight of a mixture of low density polyethylene (Hanhwa Petrochemical, LDPE 737, Tm = 103 ° C) and ethylene vinyl acetate (Hanhwa Petrochemical, EVA 1125, Tm = 80 ° C), 70.00% magnesium hydroxide, 5.00% calcium oxide, dispersant 3.00 % By weight, 5.00% by weight of blowing agent [F-190D, Matsumoto Yushi-Seiyaku Co., Ltd.] was mixed with 0.20% by weight of a mixture of an antioxidant and a heat stabilizer in a kneader (75L) at 140 ° C, and then uniaxially kneaded. Prepared on pellet through an extruder.

Example 7

16.80 wt% of thermoplastic polyolefin (Basell, Softell CA02A, Density = 0.870g / cm3), 68.00 wt% of magnesium hydroxide, 5.00 wt% of calcium oxide, 5.00 wt% of dispersant, blowing agent [F-190D, Matsumoto Yushi-Seiyaku Co., Ltd 5.00% by weight was added to a kneader (75L) at 150 ° C. together with 0.20% by weight of a mixture of antioxidants and heat stabilizers, followed by melt kneading to prepare pellets through a single screw extruder.

Comparative Example 1

21.80% by weight of a mixture of low density polyethylene (Hanhwa Petrochemical, LDPE 737, Tm = 103 ° C) and ethylene vinyl acetate (Hanhwa Petrochemical, EVA 1125, Tm = 80 ° C), 70.00% magnesium hydroxide, 5.00% calcium oxide, dispersant 3.00 The weight percent was placed in a kneader (75 L) at 140 ° C with 0.20 weight percent of a mixture of antioxidant and heat stabilizer and melt kneaded, then prepared into pellets via a single screw extruder.

Comparative Example 2

Polyolefin resin and flame retardant consisting of 10% by weight of linear low density polyethylene (LLDPE, MI = 20, density = 0.924) [JL210, SK Corporation] and 20% by weight of ethylene copolymer [Engage 8200, DuPont-Dow] based on the total resin composition weight 65% by weight of phosphorus magnesium hydroxide [Magshield S] was placed in a 110 liter capacity kneader mixer [Fine Machine] with a temperature of 150 ° C. and melt kneaded for about 13 minutes. Then, 5 wt% of a light filler (Bulk Density 0.16 ~ 0.20g / cm3, average particle size: 90㎛) [SB407, Samson Co., Ltd.] was added and kneaded for about 2 minutes and discharged to maintain 150-170 ° C. A non-halogen flame retardant polyolefin resin composition on pellets was prepared by passing through a 150 mm single screw extruder [Fine Machine].

Comparative Example 3

19.80% by weight of a mixture of low density polyethylene (Hanhwa Petrochemical, LDPE 737, Tm = 103 ° C) and ethylene vinyl acetate (Hanhwa Petrochemical, EVA 1125, Tm = 80 ° C), 50.00% by weight of magnesium hydroxide, light filler (Seokyung CMT, MSD- 1000, Bulk Density 0.19 g / cm 3, Average particle size 5 μm) 20.00% by weight, 5.00% by weight calcium oxide, 5.00% by weight dispersant were added to a kneader (75L) at 140 ° C with 0.20% by weight of a mixture of antioxidant and heat stabilizer. After melt kneading, the pellets were prepared via a single screw extruder.

The extruded formability was evaluated using the physical property analysis and the sheet molding machine for the above Examples and Comparative Examples, and the results are summarized below.

Table 2: Physical Properties of Compositions According to Examples and Comparative Examples of the Present Invention

TABLE 2

division		importance	The tensile strength	Elongation at Break	Flexibility	Extrusion Productivity	Heat deflection	Bank formation	Flame retardant class 2
		-	Kgf / ㎠	%
Example 1	Before firing	1.697	120.8	9.8	O	O	O	O	pass
	After firing	0.778	14.8	5.3
Example 2	Before firing	1.707	131.8	7.1	O	O	O	O	pass
	After firing	0.588	17.4	6.8
Example 3	Before firing	1.233	81.6	10.3	O	O	O	O	pass
	After firing	0.506	11.4	13.5
Example 4	Before firing	1.655	54.3	69.5	O	△	O	O	pass
	After firing	0.774	29.7	34.5
Example 5	Before firing	1.685	83.3	43.1	O	O	O	O	pass
	After firing	1.118	31.5	50.2
Example 6	Before firing	1.710	114.8	4.5	×	×	O	×	pass
	After firing	0.389	*	*
Example 7	Before firing	1.655	71.8	18.2	O	O	O	△	pass
	After firing	0.570	7.1	5.6
Comparative Example 1	-	1.699	127.0	7.8	O	O	O	O	pass
Comparative Example 2	-	1.460			O	×	O	O	pass
Comparative Example 3	-	1.658	129.2	7.9	O	O	O	O	pass

※ Specimen manufacture

      Before foaming: 140 ℃ / Press Molding, After foaming: 200 ~ 230 ℃ / Press Molding

      *: Not measurable O: Excellent △: Suitable ×: Not suitable

As shown in Table 2, when the blowing agent (thermally expandable microcapsules) is used, the weight of the material can be effectively reduced without loss of non-combustibility, and the problem of screw wear due to the use of the existing lightweight filler can be effectively improved.

An example of a manufactured product including the composition according to the present embodiment is an aluminum composite panel used in a building material or as an exterior material. The aluminum composite panel has a multilayer structure in which aluminum, an adhesive layer, a core, an adhesive layer, and aluminum are sequentially formed as mentioned in the prior art. Here the core material is made to include the composition provided in the above-described embodiment is characterized by the present product.

On the other hand, the present invention is not limited to the described embodiments, it is obvious to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications or variations will have to belong to the claims of the present invention.

Claims (5)

15 to 35 wt% thermoplastic polyolefin;

60 to 80 wt% non-halogen flame retardant;

Consists of 0.1 to 5.0% by weight of blowing agent

The thermoplastic flame-retardant resin composition, characterized in that the blowing agent is foamed to maintain its specific gravity below 1.35.

The method of claim 1, wherein the non-halogen flame retardant is any one or a mixture of magnesium hydroxide, aluminum hydroxide, magnesium carbonate, melamine cyanurate, red, ammonium polyphosphate, melamine phosphate, melamine polyphosphate Flame retardant resin composition.

The thermoplastic flame retardant resin composition according to claim 1 or 2, wherein the blowing agent is a thermally expandable microcapsule.

 In a molded article sequentially laminated in the order of aluminum, an adhesive layer, a core material, an adhesive layer, and aluminum, the core material is molded by containing the composition of any one of claims 1 to 3.

The aluminum composite panel molding of claim 4, wherein the composition is molded into the core material while maintaining 210 ° C. 230 ° C. to obtain an optimum degree of foaming.

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