KR20110138011A - Flame retardent resine composition for aluminum composite panel and the method of manufacturing it - Google Patents
Flame retardent resine composition for aluminum composite panel and the method of manufacturing it Download PDFInfo
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- KR20110138011A KR20110138011A KR1020100058081A KR20100058081A KR20110138011A KR 20110138011 A KR20110138011 A KR 20110138011A KR 1020100058081 A KR1020100058081 A KR 1020100058081A KR 20100058081 A KR20100058081 A KR 20100058081A KR 20110138011 A KR20110138011 A KR 20110138011A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/016—Flame-proofing or flame-retarding additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
- E04C2/30—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the shape or structure
- E04C2/34—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the shape or structure composed of two or more spaced sheet-like parts
- E04C2/36—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the shape or structure composed of two or more spaced sheet-like parts spaced apart by transversely-placed strip material, e.g. honeycomb panels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
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Abstract
Description
The present invention relates to a flame-retardant resin composition used in the core material of an aluminum composite panel, and more particularly, linear low density polyethylene (LLDPE) in which vinyltrimethoxy silane (VTMS) is grafted; Polyisobutylene succinic anhydride (PIBSA) to which vinyl trimethoxysilane (VTMS) is grafted; It relates to a flame retardant resin composition for core material of an aluminum composite panel composed of a mixture of 5 wt% of a silane crosslinking catalyst masterbatch with respect to 95 wt% of a flame retardant resin composition composed of an inorganic metal hydroxide.
Aluminum composite panel refers to a building material used for interior and exterior decoration of high-rise buildings in which cores composed of PE or flame-retardant PE are bonded between two layers of aluminum plates by an adhesive film or the like.
Aluminum composite panel is composed of 5 layers of [Aluminum / Adhesion Layer / Core Material / Adhesion Layer / Aluminum], which is a 3mm thick aluminum plate, which has a high cost burden and high specific gravity. This is because instead of reducing the thickness to 0.5mm or less, a cheaper plastic material is used to bond the aluminum plate as a core material.
The aluminum composite panel has a specific gravity of 1.2 to 1.5, which is about 40% lighter than an aluminum disc of the same thickness. Since the aluminum composite panel has a very good balance of weight and a gorgeous appearance, the utilization of the aluminum composite panel is increasing as interior and exterior materials of high-rise buildings.
The core material of the aluminum composite panel is generally manufactured based on low density polyethylene, using magnesium hydroxide as a flame retardant, and including a compatibilizer such as an antioxidant, a colorant, a moisture absorbent, and the like. In order to secure the flame retardancy of the core material in case of fire, a flame retardant resin composition containing 60 to 70% by weight of non-halogen inorganic flame retardant may be used.
However, in the case of the core material reinforced with flame retardancy, when the overall panel is manufactured using an excessive amount of inorganic flame retardant and a compatibilizer, problems of extrusion workability are generated, and the problem that the firmness of the adhesion between the core material and the aluminum plate is remarkably deteriorated. have.
In general, in an aluminum composite panel, linear low density polyethylene (LLDPE) grafted with maleic anhydride (MA) or ethylene vinyl grafted with MA is used as a core material composition for adhesion to an aluminum plate. Acetate (EVA, ethylene vinyl acetate) is used. Looking at the literature there may be mentioned Patent No. 10-851599, which uses MA-g-LLDPE as a core material composition for aluminum composite panel.
The more the amount of the MA-g-LLDPE or MA-g-EVA used, the greater the adhesive strength between the aluminum panel and the core material. However, as the content of these materials increases, the compatibility with inorganic metal hydroxides increases, leading to remarkable processability. There is a problem that reduces the manufacturing cost rises.
The present inventors applied a silane crosslinking method after various studies in order to improve such a problem, showing the same adhesive strength as that of the existing core material composition, but also very excellent in workability for a new aluminum composite panel that can significantly reduce the manufacturing cost The flame-retardant resin composition has been developed.
The present invention is a top priority to solve the degradation of workability, which is a problem of MA-g-LLDPE or MA-g-EVA used in the core of the conventional aluminum composite panel.
In order to solve the above problems, the present invention is to provide a flame-retardant resin composition that can be used in the core material of the aluminum panel.
In order to solve the above problems,
In the composition for core material of aluminum composite panel,
The core composition is composed of a flame retardant resin composition 95% by weight and silane crosslinking catalyst masterbatch 5% by weight
The flame retardant resin composition
VTMS-g-LLDPE (linear low density polyethylene (LLDPE) grafted with Vinyltrimethoxy Silane (VTMS));
VTMS-g-PIBSA (polyisobutylene succinic anhydride (PIBSA) grafted with vinyltrimethoxysilane (VTMS));
An aluminum composite panel core material composition comprising a non-halogen-based flame retardant is used as the main means for solving the problem.
The flame retardant resin composition is 5 to 20 parts by weight of VTMS-g-LLDPE; 5-20 parts by weight of VTMS-g-PIBSA; To solve the above problems using a non-halogen flame retardant 60 to 80 parts by weight,
In addition, PIBSA used in the present invention can solve the above problems by adopting 5 to 10% by weight of maleic anhydride (MA).
When the adhesive layer for aluminum panel of the present invention is used, compared with the core material using MA-g-LLDPE or MA-g-EVA as a flame retardant resin composition, the effect of initial adhesion between aluminum plates is similar, but the workability is remarkably excellent. As time passes, an aluminum composite panel having an effect of improving adhesive strength may be manufactured.
The present invention will be described in more detail with reference to the following examples. The terms used throughout the specification of the present invention are terms set in consideration of functions, and they may vary according to the intention or custom of the producer, and the definition should be made based on the contents throughout the present specification. In addition, the present invention may be variously modified and changed by those skilled in the art, and such modifications and variations should be interpreted as falling within the protection scope of the present invention.
The composition for core material for aluminum composite panel of the present invention
The core composition is composed of a flame retardant resin composition 95% by weight and silane crosslinking catalyst masterbatch 5% by weight
The flame retardant resin composition
VTMS-g-LLDPE (linear low density polyethylene (LLDPE) grafted with Vinyltrimethoxy Silane (VTMS));
VTMS-g-PIBSA (polyisobutylene succinic anhydride (PIBSA) grafted with vinyltrimethoxysilane (VTMS));
Non-halogen-based flame retardant; is composed of a core material composition of the aluminum composite panel.
Specific component ratio of the flame retardant resin composition is 5 to 20 parts by weight of VTMS-g-LLDPE; 5-20 parts by weight of VTMS-g-PIBSA; Non-halogen flame retardant 60 to 80 parts by weight.
In addition, the non-halogen-based flame retardant is magnesium hydroxide, aluminum hydroxide, zinc stannate, molybdenum tartarate, magnesium carbonate, melamine cyanurate, red, ammonium polyphosphate (APP), melamine phosphate (MP), melamine polyphosphate (MPP) is selected from.
In addition, the polyisobutylene succinic anhydride (Polyisobnutylene Succinic Anhydride, PIBSA) is a liquid type modified PIBSA containing 5 to 10% by weight, preferably 8% by weight of maleic anhydride (MA) is preferably used. good.
In addition, a variety of additives such as inorganic fillers, colorants, paraffin waxes, adhesive tackifiers and the like may be used in the core composition of the present invention.
The flame retardant resin compositions VTMS-g-LLDPE and VTMS-g-PIBSA used in the present invention are prepared through the following silane crosslinking reaction.
In the silane crosslinking method, a silane compound (Vinyltrimethoxy Silane: VTMS) is first graded in polyethylene to make a product in one step, and the crosslinking reaction is caused by leaving the product in a water state or heating.
In brief, this crosslinking reaction causes the peroxide to decompose to produce radicals in the chains of polyethylene, and then the silane compound and the free groups react secondaryly to cause grafting. The grafted silane compound is crosslinked by water and a crosslinking accelerator.
This is a chemical crosslinking method in which molding and crosslinking reactions are separated. Grafting of vinyltrimethoxyethoxy silane as a crosslinking agent on polyethylene forms a uniform molded article, and the crosslinking reaction is caused by leaving it in the presence of water. At this time, a small amount of dicumyl peroxide is added as a radical initiator and a catalyst such as dibutyltin-dilaurate is used to promote the crosslinking reaction.
By doing so, the crosslinking reaction is not performed in the molding process, so that a general polyethylene extrusion device or compounding device may be used as it is.
Organosilicon compounds having Si—H bonds are used to introduce various organic groups into silicon compounds by addition of hydrogen-siliconization reactions to organic compounds having unsaturated bonds of carbon and carbon. This hydrogen silicide requires a catalyst, and precious metal compounds such as metal platinum or chloroplatinic acid are used as catalysts. The most common and widely used catalyst is chloroplatinic acid, dissolved in isopropanol.
In addition, depending on the characteristics of the organic unsaturated compound to which trichlorosilane is added, another catalyst may be advantageous than the platinum compound as a catalyst. Catalysts used in the hydrogen silicide reaction may include nickel, rhodium, ruthenium, copper, lead, etc. in addition to precious metals such as platinum and palladium.
It is also known that organic compounds, not metals or inorganics, are used as catalysts. Examples of organic materials used as catalysts are known to have catalytic activity such as triethylamine, tritenylphosphine, dimethylformamide, and the like. (E.Y Lukevites and M, G. Voronkov, Organic Insertion Reactions of Group IV Elements, Consultants Gureau, New York, 1966).
The cross-linking process by silane is alkoxy silyl group forming the side chain of polyethylene and is bonded in the presence of water after being grafted with a crosslinking agent and a crosslinking catalyst. The apparatus may be simpler than in other cases since the crosslinking reaction is refluxed by standing in the presence of water or steam for a predetermined time.
Organosilanes are commonly used as coupling agents and commercially available in a variety of products. Among them, a vinyl silane mainly used for crosslinking polyethylene is CH 2 = CH- group attached to a silicon atom and is easily grafted to polyethylene with the aid of a radical initiator.
VTMS added for the crosslinking reaction is preferably 0.25 to 5.0% by weight, more preferably 0.5 to 2.5% by weight relative to LLDPE and PIBSA. When the content of VTMS is less than 0.25% by weight, it is difficult to impart adhesive performance. When the content of VTMS is more than 5.0% by weight, various problems occur such that the reaction efficiency decreases, discoloration occurs excessively, and unreacted VTMS remains excessive.
Graft reaction initiators that can be used to graf the VTMS to LLDPE and PIBSA include dicumyl peroxide, acyl peroxide, dialkyl or aralkyl peroxide, peroxyester, hydroperoxide, ketone peroxide, One or more than one belonging to the group such as azo compound may be selected.
The graft reaction initiator is preferably added in an amount of 0.001 to 1.0% by weight, preferably 0.1 to 0.2% by weight based on the entirety of LLDPE and PIBSA, which are basic resins. If the amount of the initiator is less than 0.001% by weight, it is difficult to uniformly disperse the grafting monomer, so that the grafting reaction is difficult to occur, and when it exceeds 1.0% by weight, the crosslinking reaction of the base resin occurs severely with the grafting reaction, resulting in melt flowability. Many problems arise, such as worsening of the gel and severe gel development.
In the present invention, by using the initiator is supported on the porous polypropylene powder resin at a concentration of 0.1 to 0.2% by weight to prevent partial crosslinking due to undispersed dispersion of the initiator can minimize gel generation.
The polyisobutylene succinic anhydride (PIBSA) used in the present invention is an organic compound having a structure of the formula [I], and is composed of a polybutene having a non-polar structure in its main chain and a maleic anhydride structure having a terminal polarity. It is useful as a compatibilizer and is especially useful for kneading a nonpolar polymer and an inorganic filler. It is also known that maleic anhydride at the end is acidic and has an excellent bactericidal effect.
[Formula I: structural formula of PIBSA]
The present invention will be described in more detail with reference to the following examples.
Example 1 Preparation of Core Material Using VTMS-g-LLDPE and VTMS-g-PIBSA
0.52 kg of vinyltrimethoxy silane (VTMS) in a mixture of 6.75 kg of linear low density polyethylene (Hanhwa Petrochemical, LLDPE 7635, Tm = 125 ° C) and 0.52 kg of polyisobutylene succinic anhydride (Daelim Industry, PIBSA) A mixture of VTMS-g-LLDPE and VTMS-g-PIBSA was prepared by uniformly mixing 30 g of Dicumyl Peroxide (DCP), followed by dry blending and extrusion using a W & P Twin Extruder.
3.25 kg of magnesium hydroxide as a flame retardant was added to 1.75 kg of the base polymer, which was then compounded using Kneader (3 L), and pelletized using a pelletizer.
Thereafter, 0.25 kg of the masterbatch for crosslinking catalyst with the pellet was dry blended to prepare a core material composition for an aluminum composite panel.
The prepared Pellet mixture was molded into a 3 mm thick sheet, and then bonded with a 1 mm thick adhesive resin (LE-102T, Hyundai EP) at 200 ° C. and 200 psi for 30 seconds.
[Example 2]
Core composition for aluminum composite panel as in Example 1 using a mixture of 5.40 kg of linear low density polyethylene (Hanhwa Petrochemical, LLDPE 7635, Tm = 124 ° C.) and 4.05 kg of polyisobutylene succinic anhydride (Daelim Industry, PIBSA) Was prepared. Then, it was bonded with the adhesive resin in the same manner as in Example 1.
[Comparative Example: Preparation of Core Material Using Linear Low Density Polyethylene (LLDPE) Grafted with Maleic Anhydride (MAH)]
0.75 kg of linear low density polyethylene (Hanhwa Petrochemical, LLDPE 7635, Tm = 124 ° C), pilot weight of 0.99 kg of linear low density polyethylene (MA-g-LLDPE) grafted with maleic anhydride, 3.25 kg of magnesium hydroxide, and 10 g of antioxidant After compounding in the kneader (3L), it was pelletized using a Pelletizer. Then, it adhere | attached with adhesive resin similarly to Example 1.
The results of evaluating the adhesive strength over time of the core material composition prepared in Examples 1 and 2 and Comparative Examples are shown through the following table.
(N / 25mm)
In Table 1, the core material compositions of Examples 1 and 2 show that the workability (MIF / MIE) is significantly improved compared to the core material composition of Comparative Example 1. In the case of adhesive strength, initially the core composition of Comparative Example 1 was superior to Examples 1 and 2, but became similar with time, and after 60 days, the core compositions of Examples 1 and 2 were comparative examples. It turned out to be much better than the core composition of 1.
Claims (4)
The core composition is composed of a flame retardant resin composition 95% by weight and silane crosslinking catalyst masterbatch 5% by weight
The flame retardant resin composition
VTMS-g-LLDPE (linear low density polyethylene (LLDPE) grafted with Vinyltrimethoxy Silane (VTMS));
VTMS-g-PIBSA (polyisobutylene succinic anhydride (PIBSA) grafted with vinyltrimethoxysilane (VTMS));
Non-halogen flame retardant; composition for core material of aluminum composite panel comprising
The non-halogen-based flame retardant is magnesium hydroxide, aluminum hydroxide, zinc stannate, molybdenum stannate, magnesium carbonate, melamine cyanurate, red, ammonium polyphosphate (APP), melamine phosphate (MP), melamine polyphosphate (MPP) Aluminum composite panel core material composition characterized in that is selected from
The flame retardant resin composition
5-20% by weight of VTMS-g-LLDPE; 5-20% by weight of VTMS-g-PIBSA; Aluminum composite panel core material composition, characterized in that consisting of non-halogen-based flame retardant 60 ~ 80% by weight
The polyisobutylene succinic anhydride (Polyisobnutylene Succinic Anhydride, PIBSA) is a composition for core material of aluminum composite panel, containing 5 to 10% by weight of maleic anhydride (Maleic Anhydride, MA)
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| KR1020100058081A KR20110138011A (en) | 2010-06-18 | 2010-06-18 | Flame retardent resine composition for aluminum composite panel and the method of manufacturing it |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150054182A (en) * | 2013-11-11 | 2015-05-20 | 홍성산업 주식회사 | Aluminium composite panel for a backplate of display device |
| CN105482240A (en) * | 2013-09-29 | 2016-04-13 | 江苏理工学院 | Preparation method of halogen-free flame-retardant linear low-density polyethylene material |
| KR20160139947A (en) | 2015-05-29 | 2016-12-07 | 신호테크 주식회사 | Environment Friendly and Fire-Retardant Material EVA Panel |
| WO2019238957A1 (en) * | 2018-06-15 | 2019-12-19 | Borealis Ag | Flame retardant composition |
| KR20200023374A (en) * | 2017-06-29 | 2020-03-04 | 다우 글로벌 테크놀로지스 엘엘씨 | Moisture Cured Wire and Cable Structure |
| WO2021092167A1 (en) * | 2019-11-06 | 2021-05-14 | Berry Global, Inc. | Wrap film with polyisobutylene succinic anhydride |
| CN117327347A (en) * | 2023-09-19 | 2024-01-02 | 江苏海聚新材料科技有限公司 | Flame-retardant polypropylene and preparation method and application thereof |
-
2010
- 2010-06-18 KR KR1020100058081A patent/KR20110138011A/en active IP Right Grant
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482240A (en) * | 2013-09-29 | 2016-04-13 | 江苏理工学院 | Preparation method of halogen-free flame-retardant linear low-density polyethylene material |
| CN105482240B (en) * | 2013-09-29 | 2020-06-02 | 江苏理工学院 | Preparation method of halogen-free flame-retardant linear low-density polyethylene material |
| KR20150054182A (en) * | 2013-11-11 | 2015-05-20 | 홍성산업 주식회사 | Aluminium composite panel for a backplate of display device |
| KR20160139947A (en) | 2015-05-29 | 2016-12-07 | 신호테크 주식회사 | Environment Friendly and Fire-Retardant Material EVA Panel |
| KR20200023374A (en) * | 2017-06-29 | 2020-03-04 | 다우 글로벌 테크놀로지스 엘엘씨 | Moisture Cured Wire and Cable Structure |
| WO2019238957A1 (en) * | 2018-06-15 | 2019-12-19 | Borealis Ag | Flame retardant composition |
| CN115746609A (en) * | 2018-06-15 | 2023-03-07 | 博里利斯股份公司 | Flame retardant composition |
| WO2021092167A1 (en) * | 2019-11-06 | 2021-05-14 | Berry Global, Inc. | Wrap film with polyisobutylene succinic anhydride |
| US11530282B2 (en) | 2019-11-06 | 2022-12-20 | Berry Global, Inc. | Wrap film with polyisobutylene succinic anhydride |
| CN117327347A (en) * | 2023-09-19 | 2024-01-02 | 江苏海聚新材料科技有限公司 | Flame-retardant polypropylene and preparation method and application thereof |
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