JPH06299007A - Flame-retardant polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain a flame-retardant polyolefin resin composition which scarcely suffers bleeding of a flame retardant and is improved in flame retardancy by using a polyolefin resin and a specified compound as the constituents. CONSTITUTION:A tetrabromobisphenol A epoxy resin of an epoxy equivalent of at most 1528 is reacted with tribromophenol to give a compound of formula I (wherein X is a group of formula II; Y is a group of formula III; R is X or Y-H; and n is 1 to 5) having a bromine content of at most 55.0%. 100 pts.wt. polyolefin resin is mixed with 0.2-40 pts.wt. compound of formula I and, if necessary, additives such as a stabilizing agent, a coloring agent, an ultraviolet absorber, a lubricant, and antistatic agent and an extender.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polyolefin resin composition, and more particularly to a flame-retardant polyolefin resin composition having less flame-retardant bleed-out and excellent flame-retardant performance.

[0002]

2. Description of the Related Art Polyolefin resin is lightweight, has high strength, is excellent in water resistance, chemical resistance, and electrical insulation, and is easy to mold and process. Therefore, it is used as a building material, a material for electric appliances, and a vehicle part. It is widely used for automobile interior materials, electric wire coating materials, and various other industrial and household products. However, polyolefins have the disadvantage of being easy to burn. For this reason, many methods for flame-retarding polyolefins have been proposed.

The most widely used conventional flame-retardant method is a method of adding a halogen-containing compound and antimony oxide to a polyolefin. Examples of the halogen compound include tetrabromobisphenol A, hexabromocyclododecane, bis-dibromopropyl ether of tetrabromobisphenol A, bis-dibromopropyl ether of tetrabromobisphenol sulfone, and tris.
2,3-dibromopropyl isocyanurate, bis-tribromophenoxyethane, hexabromobenzene, decabromodiphenyl ether and the like are known. However, as a drawback of these compounds, for example, when tetrabromobisphenol A is used, discoloration occurs due to heat during molding, and when decabromodiphenyl ether is used, it does not dissolve in polyolefin and the dispersibility deteriorates. However, when hexabromocyclododecane was used, there was a problem of bleeding out violently.

[0004]

The present inventors have completed the present invention as a result of intensive studies to solve the drawbacks of conventional flame retardants. The present invention relates to a general formula X-having a bromine content of 55.0% or more with respect to 100 parts by weight of a polyolefin resin.
_{CH 2 CH (OH) CH 2} - _{[Y-CH 2 CH (OH)} CH 2 ] n -R
(A) (where X is

[Chemical 3] Y is

[Chemical 4] , R represents X or Y-H, and n represents 1 to 5)
A flame-retardant polyolefin resin composition containing 0.2 to 40 parts by weight of the compound shown by.

The compound represented by the general formula A according to the present invention has good compatibility with polyolefin and can impart excellent flame retardancy to polyolefin. Further, it has an excellent feature that the bleed-out of the polyolefin on the surface of the material is extremely small, and the gloss, hue, and flame retardancy of the surface of the polyolefin hardly change with time.

The polyolefin used in the composition of the present invention includes olefin polymers such as polyethylene, polypropylene, poly-1-butene, poly-1-pentene and the like, and mixtures thereof, ethylene, propylene, 1-butene, 1
-Copolymers such as pentene and mixtures thereof, ethylene-propylene rubber (EPM, EPR), ethylene-propylene-diene terpolymer (EPDM, EPD, EPT)
And other polyolefin-based elastomers and mixtures thereof, mixtures of polyolefin-based elastomers with olefin polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers, copolymers with other vinyl-based monomers containing olefin as the main component, and others. It can be arbitrarily selected from a mixture of two or more of these. Further, these polyolefins may contain stabilizers, colorants, weathering agents (ultraviolet absorbers), lubricants, antistatic agents, extenders, and other additives.

The flame retardant (A) effective for the composition of the present invention is obtained by the reaction of tetrabromobisphenol A type epoxy resin and tribromophenol. For example, among diglycidyl ethers of tetrabromobisphenol A and compounds having epoxy groups at both ends obtained by the reaction of tetrabromobisphenol A and epichlorohydrin, the epoxy resin having an epoxy equivalent of 1528 or less, preferably 1000 or less is reacted with tribromophenol. And the epoxy equivalent is 1228 or less, preferably 100
It is a compound having a bromine content of 55.0% or more obtained by a reaction of an epoxy resin of 0 or less with tribromophenol and tetrabromobisphenol A.

Examples of compounds effective in the present invention are shown below. _{X- CH 2 CH (OH) CH} 2 - _{[Y-CH 2 CH (OH)} CH 2 ] _{n -X (I) X- CH 2} CH (OH) CH 2 - _{[Y-CH 2 CH (OH)} CH ₂ ] n -YH (II) In the formula, X and Y have the above-mentioned meanings. In the compound of formula (I), when n is 1, the bromine content is 60.6.
%, When n is 2, the bromine content is 58.3%, when n is 3, the bromine content is 57.1%, when n is 4, the bromine content is 56.4%, n is 5 In the case of, the bromine content is 55.
9%. In the compound of formula (II), n is 1
, The bromine content is 57.4%, when n is 2, the bromine content is 56.3%, and when n is 3, the bromine content is 5%.
When 5.6% and n is 4, the bromine content is 55.2%.

The bromine content of the flame retardant (A) used in the present invention is 55.0% or more, preferably 56% or more.
If the bromine content is 55% or less, the flame retardant performance deteriorates. The flame retardants of the formulas [I] and [II] can be used alone or in a mixed state. The composition of the present invention contains 0.2 to 40 parts by weight of the flame retardant (A) with respect to 100 parts by weight of the polyolefin resin. If this ratio is less than 0.2 parts by weight, the flame retardancy of the resulting composition is insufficient. On the other hand, when the content is more than 40 parts by weight, there is a disadvantage that the physical properties of the composition, particularly the strength are deteriorated. The composition of the present invention may contain, in addition to the polyolefin resin and the bromine compound (A), antimony oxide such as antimony trioxide or antimony pentoxide, in which case the addition amount of the bromine compound (A) is smaller. Good.

Conventional mixing methods can be utilized to produce the compositions of the present invention. That is, the polyolefin powder and pellets and the flame retardant can be mixed and melt-mixed using a kneader, a screw type extruder, a Banbury mixer, a mixing roll and the like. The composition of the present invention is a sheet, film, tube, pipe, plate, fiber,
It can be molded into any other shape,
These can be used as materials for civil engineering and construction, materials for electric appliances, materials for vehicles, interior products, clothing products, and other miscellaneous goods products.

[0011]

EXAMPLES The characteristics of the flame-retardant polyolefin resin composition of the present invention will be described in more detail with reference to examples. The combustion tests in the examples are UL-94, OI (JIS K7210) and F.
-It carried out by the method according to MVSS302 and JIS D-1201. The bromine content was measured by the flask combustion method. Synthesis Example 1 ([I] type, compound having n = 1 as a main component) Tribromophenol 662 g in 656 g (1 mol) of diglycidyl ether of tetrabromobisphenol A
(2 mol) and 0.5 g of tributylamine were added, and the mixture was reacted in a nitrogen stream at 120 to 130 ° C. for 8 hours, then 150
Reacted at ~ 160 ° C for an additional 3 hours. After the reaction was completed, the product was taken out on a stainless steel vat, cooled and pulverized to obtain a pale yellow crude powder (Compound 1). Softening point 94-101 ° C, bromine content 60.5%. Synthesis Example 2 ([II) type, a compound having n = 1 as a main component) Tetrabromobisphenol A diglycidyl ether 656 g (1 mol) and tribromophenol 331 g
(1 mol) and tributylamine 0.5 g were added, and after reacting at 120 to 130 ° C. for 5 hours in a nitrogen stream, tetrabromobisphenol A 544 g (1 mol) was added to give 160
The reaction was carried out at ~ 170 ° C for 6 hours. After the reaction, the product was taken out on a stainless steel vat, cooled and pulverized to obtain a pale yellow crude powder (Compound 2). Softening point 118-127 ° C, bromine content 5
7.2%.

Synthesis Example 3 ([I] type, compound having n = 2 as a main component) 1260 g (1 mol) of tetrabromobisphenol A type epoxy resin (epoxy equivalent 630) was added with 662 g (2 mol) of tribromophenol and tri. Butylamine 0.7
g, and in a nitrogen stream at 120 to 130 ° C. for 8 hours, 15
The reaction was continued at 0 to 160 ° C. for 5 hours. After completion of the reaction, the product was taken out on a stainless steel vat, cooled and pulverized to obtain a pale yellow crude powder (Compound 3). Softening point 104-113 ° C, bromine content 58.1%.

Synthesis Example 4 (Compound having [I] type, n = 3 as a main component) Tetrabromobisphenol A type epoxy resin (epoxy equivalent 930) 930 g (0.5 mol) and tribromophenol 331 g (1 mol) And tributylamine 0.
6g is added, and it is 120-130 degreeC for 8 hours in nitrogen stream for 1 hour.
The reaction was carried out at 60 to 170 ° C for 7 hours. After the reaction was completed, it was taken out on a stainless steel vat, cooled and pulverized to obtain a pale yellow crude powder (Compound 4). Softening point 108-118 ° C, bromine content 57.1%.

Synthesis Example 5 (for Comparative Example) Tetrabromobisphenol A4 was added to 656 g (1 mol) of diglycidyl ether of tetrabromobisphenol A.
35 g (0.8 mol) and tribromophenol 66 g
(0.2 mol) As a solvent, 500 g of dioxane and 1.5 g of tributylamine were added, and the mixture was added in a nitrogen stream to give 101-102.
Reacted at 20 ° C. for 20 hours. After the reaction, the solvent was removed under reduced pressure (15 mmHg). After cooling, the mixture was pulverized to obtain a pale yellow crude powder (Compound 5). Softening point 169-177 ° C, bromine content 5
3.6%.

Synthesis Example 6 (For Comparative Example) To 1260 g (1 mol) of tetrabromobisphenol A type epoxy resin (epoxy equivalent 630), 400 g (0.735 mol) of tetrabromobisphenol A and 0.6 g of tributylamine were added, and a nitrogen stream was added. Medium 160-180
Reacted at 9 ° C for 9 hours. After the reaction, the mixture was cooled and pulverized to obtain a pale yellow crude powder (Compound 6). Softening point 155 to 162 ° C, bromine content 52.4%.

Example 1 100 parts by weight of commercially available polyethylene pellets (Sumikasen F-101 manufactured by Sumitomo Chemical Co., Ltd.) were mixed with 10 parts by weight of the compound prepared in Synthesis Example and 4 parts by weight of antimony trioxide at 150 ° C. using a mixing roll. The mixture was kneaded in, and press-molded at 200 ° C. to form a flat plate having a thickness of 1.5 mm. The flame retardant performance was evaluated by UL-94 and OI.

[0017]

[Table 1]

Example 2 100 parts by weight of a commercially available thermoplastic polyolefin elastomer (Mitsui Petrochemical Co., Ltd., Mirastomer 8030N) were mixed with 13 parts by weight of the compound prepared in the synthesis example and 4 parts by weight of antimony trioxide by a mixing roll. The mixture was kneaded at 0 ° C and press-formed at 200 ° C to form a flat plate having a thickness of 1.5 mm. The flame retardant performance was evaluated by UL-94 and OI.

[0019]

[Table 2]

Example 3 100 parts by weight of commercially available polypropylene pellets (Noblen W-101 manufactured by Sumitomo Chemical Co., Ltd.) were mixed with 20 parts by weight of the compound prepared in the synthesis example and 7 parts by weight of antimony trioxide at 160 ° C. using a mixing roll. The mixture was kneaded in, and press-molded at 200 ° C. to form a flat plate having a thickness of 1.5 mm. The flame retardant performance was evaluated by UL-94 and OI.

[0021]

[Table 3]

Example 4 100 parts by weight of a commercially available thermoplastic polyolefin elastomer (Mitsui Petrochemical Co., Ltd., Mirastomer 5030B) was mixed with 1 part of the compound prepared in the synthesis example and a conventional brominated flame retardant.
5 parts by weight and 5 parts by weight of antimony trioxide were kneaded using a mixing roll at 160 ° C. and press-molded at 200 ° C. to form sheets with thicknesses of 0.3 mm and 0.5 mm, and flame resistance and bleeding. Out was evaluated. The flame-retardant performance was evaluated on a sample having a sheet thickness of 0.3 mm by the horizontal method according to F · MVSS302 method and JIS D1201. The bleed-out was performed by suspending a sample having a sheet thickness of 0.5 mm and a size of 3 cm × 8 cm in a film clip for 72 hours in an oven at 60 ° C., observing the surface of the sheet, and evaluated as follows. ◎: No bleed-out ○: Slight bleed-out ×: Bleed-out XX: Violent bleed-out Conventional flame retardant used in Comparative Example A: Hexabromocyclododecane B: Bisdibromopropyl ether of tetrabromobisphenol S C: bisdibromopropyl ether of tetrabromobisphenol A D: 1,2-bis (tribromophenoxy) ethane E: tris (2,3-dibromopropyl) isocyanurate

[0023]

[Table 4]

[0024]

[Table 5]

[0025]

[Table 6]

Claims (1)

[Claims] 1. A general formula of the above bromine content 55.0% relative to the polyolefin resin 100 parts by _{X- CH 2 CH (OH) CH} 2 - _{[Y-CH 2 CH (OH)} CH 2 ] n -R ( A) (where X is Y is , R represents X or Y-H, and n represents 1 to 5)
A flame-retardant polyolefin resin composition containing 0.2 to 40 parts by weight of the compound shown by.