KR20060060796A - Flame retardant and reinforced polyester composition - Google Patents

Abstract

The present invention satisfies NFPA 130 (American Fire Prevention Association Standard for Flame and Smoke in Fire Vehicles) and BS6853 (British Standard for Smoke Toxicity in Fire) by blending composite flame retardants and glass fibers in certain polyester resins. The productivity is the same as that of the existing FRP, and it improves the strength of the existing FRP resin, has excellent workability, and exhibits stable properties even under external circumstances such as working conditions. An unsaturated polyester resin composition is provided.

Description

Flame-retardant reinforced polyester resin composition {FLAME RETARDANT AND REINFORCED POLYESTER COMPOSITION}

The present invention relates to a flame-retardant reinforced polyester resin composition.

More specifically, the present invention relates to a flame-retardant polyester resin composition that can be used as interior materials for railways, aircrafts, and automobiles, and interior materials for railways, aircrafts, and automobiles using the same.

Products made of glass fiber reinforced polyester resin (abbreviated as UPRE) not only have excellent mechanical properties, low density, chemical resistance and excellent surface properties, but also low manufacturing cost, so that It is being used to replace metal materials in the building and aircraft fields.

As it can be seen from the Daegu subway disaster in February 2000, after the tragedy was found to be due to the use of materials such as vehicle interior materials that do not meet the fire safety standards, in particular, non-flammable general FRP (glass fiber reinforced plastic), Incombustibility of interior materials such as is attracting attention.

In particular, FRP boards using UPRE are mainly used as interior materials for domestic railway vehicles, but there is a problem in that they cannot satisfy the combustibility, smoke density, flame propagation, and combustion gas toxicity standards of international standards. Research and development is in progress, but practically no material has been developed.

Accordingly, the present inventors have studied unsaturated polyester resin compositions that can be safely used even in the event of a fire as interior materials for railways, automobiles, etc. As a result, composite flame retardants and glass containing aluminum hydroxide, chlorine-based flame retardants and antimony trioxide in specific unsaturated polyester resins By blending the fibers in the proper proportions, NFPA 130 (American National Fire Prevention Association's standard for overall fire safety of passenger railcar systems) regulates the flame propagation and smoke density on surfaces in the materials used to withstand fire. ) And BS6853 (British standard on the toxicity of smoke in the event of a fire in a railway vehicle), and the productivity is the same as the existing FRP, improve the strength of the existing FRP resin, workability and external conditions such as working conditions Fire-retardant reinforcement fire which shows stable property in change A saturated polyester resin composition was developed, and based on this, the present invention was completed.

FRP is an abbreviation of Fiber Reinforced Plastic and is a general term for fiber composite reinforced with fiber. Plastics as matrices are called FRP for thermosetting resins and FRTP (Fiber Reinforced Thermo Plastic) for thermoplastics.

Also, glass fiber, carbon fiber and boron fiber, which are used as reinforcing fibers, are called G (F) RP, CFRP, and BFRP, respectively. FRP usually refers to GRP.

In general, FRP refers to the production using glass fibers and unsaturated polyester (UP), and may be classified according to the molding method. FRP can be classified into heat-resistant FRP, corrosion-resistant FRP, and general FRP according to its physical properties. Recently, the use range of FRP has been expanded for structural applications requiring high strength.

There are various methods of forming the FRP. The interior plate of the railway vehicle is manufactured by a hand layering operation method.

The hand layer up method is to apply the surface resin composition of the mold and make it smooth while impregnated with a roller, and then repeat this operation until the molded article has a desired thickness. Glass fiber mat is mainly used as the reinforcing material, and various fabrics are also used depending on the strength of the product required.

The structure of the electric vehicle replacement built-in plate made by such a hand layering work method is made of a universal structure of FRP.

Gel Coat Layer Surface Mat Layer 225 Chopped Strand Mat 225 Chopped Strand Mat Yarn Cloth

The total thickness of the interior plate is about 2.5mm and the thickness of the gel coat is about 0.3mm, this structure tends to lack the strength reinforcing layer due to the rather thin form compared to the general FRP structure.

Strength reinforcing layer should be laminated to the required thickness using a mat, roving cross, etc. In the case of using a roving cross or yarn cross, it is preferable to alternately use Chopped Strand Mat.

According to the hand lay-up method, the manufacture of electric vehicle replacement interior plates is made by applying a gel coat to the surface of the mold and laminating it in the order of surface mat, chopped strand mat and yarn cross.

Yarn cross is a woven glass fiber with a beautiful appearance compared to irregular Mat, which is used for the purpose of increasing the smoothness of the back side and covering the laminated Mat to enhance the aesthetics. Mat is laminated by adding resin, but Yarn Cloth is laminated without resin as final finish.

It should be noted that the lamination of the yarn cross may cause peeling if the work cannot be done quickly after the last 225 mat.

Choped Strand Mat (hereinafter referred to as 225 Mat) has various types, but it is usually divided by weight per m ² , and 225g / m ² was used in this development.

 The use of 225Mat compensates for the thickness and is used in consideration of strength and mechanical properties. Especially, the impregnation of resin is more difficult than 225Mat, so that 225Mat is laminated on the surface mat twice in order to improve workability and product quality. It is designed as a configuration. 225Mat used CM225 manufactured by Owens Corning Korea.

The surface mat is used after the gel coat layer for the purpose of preventing the glass fibers to be laminated from being seen or protruding out of the gel coat layer and making the appearance poor. The surface mat usually has a structure in which glass fibers of 12 to 15 µm are laminated irregularly and weighs about 30 g / m ² . The surface mat is surface-treated with silane for impregnation with resin, and is composed of a part using nitrogen-based adhesive such as melamine for fixing between glass fibers.

Gel coat is the outermost layer that forms the painted surface layer for interior appearance in the interior plate, and is manufactured by using conventional unsaturated unsaturated polyester resin as a base and blended with halogenated flame retardant, so that the flame retardancy can be secured in a small amount. There was a disadvantage that the smoke concentration increase and the toxicity index did not meet the criteria.

The present inventors have recognized this problem, and while studying the resin composition that can be safely used even in the event of a fire as an interior material for railroads and automobiles, while meeting the standards for smoke concentration and toxicity index required by developed countries, specific unsaturated polyesters have been studied. By combining a composite flame retardant containing aluminum hydroxide, chlorine-based flame retardant and antimony trioxide in the resin and blending the glass fiber in an appropriate ratio according to the intended use, it satisfies the NFPA 130 and BS6853 specifications required by developed countries simultaneously, and the productivity is compared with existing FRP. The same, to improve the strength of the existing FRP resin, excellent workability, and developed a flame-retardant reinforced unsaturated polyester resin composition exhibiting a stable property even in the external situation changes, such as working conditions.

Unsaturated polyesters used as base resins of resin compositions used in gel coats are polycondensates made from saturated and unsaturated dicarboxylic acids or their anhydrides and diols. Unsaturated polyesters are cured by free radical polymerization, for example using initiators and accelerators such as peroxides.

The most important dicarboxylic acids are maleic anhydride, fumaric acid and terephthalic acid, and 1,2-propanediol is most frequently used for diols. In addition, ethylene glycol, diethylene glycol and neopentyl glycol may be used.

The crosslinking monomer is usually styrene and can be blended and copolymerized with an unsaturated polyester resin.

Among these unsaturated polyester resins, gas is not generated during pyrolysis in consideration of flame retardancy, smoke density, strength, and the like, and resins having a high CFT (char factor) are advantageous, particularly those having a chemical structure of the following Chemical Formula 1 or 2 I found that.

Epoxyacrylic Polyvinyl Ester Resin

Noblock-based vinyl ester resin

As a flame retardant used for flame retardation of the said base resin, the combination of aluminum hydroxide, a chlorine-type flame retardant, and antimony trioxide was used.

Aluminum hydroxide has the effect of suppressing the flame by generating water at high temperature, and is characterized by low smoke density.

Flame retardation of aluminum hydroxide is known to be lowered due to the cooling effect of the endothermic reaction during dehydration reaction, and to occur due to the extinguishing power through dilution of flammable gas due to the formation of incombustible layer after dehydration and generation of H ₂ O at decomposition temperature. have.

In addition, the low smoke of aluminum hydroxide, when the polymer is decomposed, the aluminum hydroxide is converted into all trans forms, and after the smoke is generated, the smoke concentration is reduced by decomposing and diluting the smoke by OH radicals produced by the decomposition of aluminum hydroxide. It is understood that.

In view of self-combustibility and low smoke density, aluminum hydroxide is preferably 150 to 200 parts by weight per 100 parts by weight of unsaturated polyester resin.

The aluminum hydroxide used has a particle average size in the range of 0.5 μm to 2.0 μm. Advantageously, aluminum hydroxide is more advantageously surface modified.

Chlorinated flame retardant is used 15 to 40 parts by weight per 100 parts by weight of unsaturated polyester resin. If the amount is less than 15 parts by weight, there is no flame retardant effect, and when 40 parts by weight or more is used, the thermal stability is impaired.

Examples of the chlorine-based flame retardant include aliphatic compounds such as chlorinated paraffin and chlorinated polyethylene, and declofurans (trade name of American Occidental Chemical), which are used together with antimony trioxide to give synergistic effect. In the present invention, chlorinated paraffin is preferably used. Chlorinated paraffin is produced by chlorination of paraffin wax or normal paraffin, and is divided into liquid products and solid products according to the molecular weight or degree of chlorination of raw materials paraffins. Solid products having a chlorine content of 50% or more are preferred in view of flame retardancy and workability.

Antimony trioxide is used in combination with the chlorine-based flame retardant to exhibit a synergistic effect, preferably from 15 to 40 parts by weight per 100 parts by weight of unsaturated polyester resin. If the amount is less than 15 parts by weight, the effect as a flame retardant aid is not sufficiently exhibited, and if the amount is larger than 40 parts by weight, defects such as deterioration of mechanical properties appear.

As antimony trioxide, the thing of purity 98% or more and particle diameter of 0.1-2 micrometers is used preferably. In particular, it is more preferable that it is 99% or more of purity, and 0.5-1.5 micrometers of particle diameters.

In addition, the fibrous inorganic filler may be added as needed to improve the heat resistance and mechanical properties of the resin composition of the present invention, it is preferable that 5 to 100 parts by weight of the fibrous inorganic filler is blended with respect to 100 parts by weight of unsaturated polyester.

As a fibrous inorganic filler, glass fiber, carbon fiber, steel fiber, asbestos, a ceramic fiber, potassium titanate whisker, boron whisker, aluminum borate whisker, calcium carbonate whisker etc. are mentioned, for example. These may be used alone or in combination of two or more.

Among these fibrous reinforcing materials, glass fibers are preferred. The glass fiber is not particularly limited as long as it is generally used for resin reinforcement.

For example, it can select and use from a long fiber type (glass roving) or a short fiber-like chopped strand, a milled fiber, etc. In addition, fibrous reinforcements such as glass fibers may be treated with a binding agent (eg, polyvinyl acetate, polyester binding agent, etc.), a coupling agent (eg, silane compound, borane compound, titanium compound, etc.), and other surface treatment agents.

The resin composition was uniformly mixed with an unsaturated polyester resin, a flame retardant, etc. using a high speed stirrer and then used as a gel coat, and laminated thereon in the order of surface mat, 225met, 225met, and yancross to obtain a laminate. .

Fire performance test was evaluated in accordance with ASTM E162 (surface flame propagation standard) and ASTM E 662 (smoke density standard) and BS 6853-Annex B2 (smoke toxicity test standard). Various mechanical properties are required for the interior of railway vehicles. Evaluation was made according to the specification.

1.ASTM E662-03 test (smoke density standard)

A test that measures the optical density of smoke generated by solid materials, which measures the attenuation of light rays by smoke (suspended solid or liquid particles) accumulated in a closed chamber due to nonflame pyrolysis and flame combustion.

Ds (1.5) and Ds (4.0) are optical densities after 1.5 minutes and 4.0 minutes, respectively, and in flame or nonflame test mode, Ds (1.5) should be ≤100 and Ds (4.0) should satisfy ≤200.

2. ASTM E162-02a Test (Surface Flame Propagation Standard)

Surface flammability test of material using radiation energy source.

Four test specimens, 6 × 18 inches in size, are dried at 60 ° C for 24 hours and maintained at a relative humidity of 50 6 5% and a temperature of 23.3 ° C prior to testing.

Each test piece was inclined at an angle of 30 degrees perpendicular to the front surface to a 12 x 18 inch gas flame incandescent panel, and was evaluated by a ignition test after being bitten by a holder. The following flame conversion index was calculated from the rate of heat generation and the propagation rate of the front flame by the material under test.

Is = Fs ㆍ Q

Is is the flame spreading index, Fs is the flame propagation factor, Q is the heat emission factor, and it must satisfy Is ≤35 to be used as a rail vehicle interior.

3. British Fire Performance Test BS 6853-ANNEX B2

Test samples of 3 mm thickness were tested to determine the weight of the toxic gas.

The smoke toxicity is defined as the sum of the R values obtained by dividing the amount of extracted poison gas from the test by the amount of poison gas in the atmosphere that has a fatal effect on life or health when breathing for 30 minutes given by the National Institute of Occupational Safety & Health (Noish).

R = ∑rx, rx = cx / fx

(cx: amount of poison gas extracted from the specimen, fx: amount of poison gas given in fx: Noish), and R≤ 1.6 must be satisfied.

4. Flexural strength, compressive strength and tensile strength acceptance criteria and test regulations of materials are as follows.

exam Electric Vehicle Interior Passing Criteria Test Regulation Flexural strength 10.5 kg / mm ² or more ASTM D790 Compressive strength 12.6 kg / mm ² or more ASTM D695 The tensile strength 7 kg / mm ² or more ASTM D638

Example 1 Test according to resin type and content of aluminum hydroxide flame retardant in resin composition used in gel coat

The resin composition was 100 parts by weight of each of the unsaturated polyesters listed in Table 1, aluminum hydroxide in the amount shown in Table 1 (particle size 1 μm, Nippon Light Metal, BF013, Japan), 33 parts by weight of paraffin X70 (Xu) having a chlorine content of 70% (Xu). Zhou Construction Machinery Group & Exp. Co., Ltd.) and 33 parts by weight of antimony trioxide (Cheil Chem HS, particle size 0.5 μm, white), and then coated with a gel coat according to the hand layup method (Owen Corning Kingdom, UK, 30g / m ² ), 225met (Owen Corning, Korea, CM225), 225met (Owen Corning, Korea, CM225), Yancross (Gangnam Precision, Korea, 200g / m ² ) It laminated and manufactured and evaluated the interior board | plate for electric vehicles.

Example Resin Type Parts by weight of aluminum hydroxide ASTM-162 ASTM-662 (D _4.0 ) One Noblelock 50 75 - 2 100 45 200 3 150 35 154 4 180 15 102 5 VE 180 20 170 Resin: Noblock: Noblock-based vinyl ester resin of formula (Viscosity 150 cp), VE: Epoxyacryl-based vinyl ester resin of formula (Viscosity 200 cp)

From the above results, it was found that the amount of aluminum hydroxide did not meet the criteria for the surface salt when the added amount was 150 parts by weight or less.

In addition, the flexural strength, the compressive strength, and the tensile strength of the resin composition of Example 4 were measured, and the results were 18.2 kg / mm ² , 16.2 kg / mm ² , and 10.4 kg / mm ² , respectively. It can be seen that the mechanical properties are satisfactory.

Furthermore, 3. The toxicity test according to the British Fire Performance Test BS 6853-ANNEX B2 showed an R value of 0.46, which satisfies the criteria of R≤1.6.

Example 2 Test for Flame Retardant Effect According to Particle Size of Aluminum Hydroxide Used as Flame Retardant in Resin Compositions Used in Gel Coat

Example 1 except that 100 parts by weight of a novolac resin of Formula 2 (viscosity 150 cps) used in Example 1 was used as the resin, and 180 parts by weight of aluminum particles having a particle size of 50 μm, 25 μm, 8 μm, or 1 μm was used. In the same manner as in the interior was made and evaluated.

Example Aluminum hydroxide particle size ASTM-162 ASTM-662 4 1 μm 15 102 6 8㎛ 15 110 7 25 μm 25 150 8 50 μm 40 205

Example 3 Test on the Flame Retardant Effect According to the Contents of Paraffin Chloride and Antimony Deep Oxide Used as Flame Retardant in Resin Compositions Used in Gel Coat

100 parts by weight of Novolac Formula 2 (viscosity 150 cps) was used as the resin, and 180 parts by weight of 1 μm of particle size was used as the aluminum hydroxide, and the same flame retardant as in Example 1 was used.

Example Paraffin chloride weight part Antimony trioxide by weight ASTM-162 ASTM-662 4 33 33 15 102 9 10 10 35 120 10 15 15 35 120 11 20 20 30 110

If paraffin chloride and antimony trioxide are more than 20 parts by weight, it can be seen that the surface flame propagation and smoke density standards are satisfied.

The unsaturated polyester flame retardant resin composition according to the present invention satisfies the advanced standards NFPA 130 and BS6853 at the same time, the productivity is the same as the existing FRP, improve the strength of the existing FRP resin, excellent workability, such as external working conditions It can be used as interior materials of automobiles, airplanes, and railway vehicles by showing stable properties even in changing situations.

Claims (8)

A flame-retardant unsaturated polyester resin composition containing 150 to 200 parts by weight of aluminum hydroxide, 15 to 40 parts by weight of chlorine-based flame retardant and 15 to 40 parts by weight of antimony trioxide based on 100 parts by weight of unsaturated polyester resin. The resin composition according to claim 1, wherein the unsaturated polyester resin has a structure represented by the following general formula (1) or (2): (Formula 1) Epoxy Acrylic Polyvinyl Ester Resin

 (Formula 2) Noblock-based vinyl ester resin

The resin composition according to claim 1, wherein the particle size of the aluminum hydroxide is 0.5 µm to 2.0 µm. The resin composition according to claim 1, wherein 5 to 100 parts by weight of the fibrous inorganic filler is further blended with respect to 100 parts by weight of the unsaturated polyester, The resin composition according to claim 1, which is used for gel coating of automobile, airplane, and railway vehicle interior plates. The resin composition according to claim 4, which is used as an interior plate of an automobile, an airplane, or a railway vehicle. Interior materials made of the flame retardant unsaturated polyester resin composition according to claim 1, wherein the test specifications Ds (1.5) ≤ 100, Ds (4) ≤ 200 (ASTM E 662), Is ≤ 35 (ASTM E 162) and R for fire. Interior material characterized by satisfying? The interior material according to claim 7, which is used as interior materials for railway vehicles.