JP4012431B2 - Flame retardant olefin resin composition - Google Patents

Description

【００３８】
実施例１〜７は、難燃性はＶ−０レベルであり、成形品のべたつきもなかった。実施例８は、難燃性はＶ−０レベルであったが、成形品のべたつきが大きく、用途によっては改善の余地がある。比較例１、２は、（Ｂ）ポリリン酸メラミンと（Ｃ）炭化剤の比率が５であるので難燃性は十分ではないが、成形品のべたつきは悪くない。比較例３、４は、ポリリン酸アンモニウム−１又は−２を配合したため、難燃性はＶ−０レベルであるが、成形品のべたつきが著しく、プレス成形時の金型汚れもひどかった。
【００３９】
【発明の効果】
本発明の組成物によれば、難燃性が優れた成形品が得られ、用途に応じてべたつきの少ない成形品を提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a flame-retardant olefin resin composition and a molded product obtained therefrom.
[0002]
[Prior art and problems to be solved by the invention]
Polyolefins are excellent in molding processability, solvent resistance and mechanical strength, and are widely used in the fields of automobile parts, electrical / electronic equipment parts, home appliances, etc. as low-specific gravity and inexpensive plastics. As a flame retardant method of polyolefin, blending of an inorganic flame retardant represented by magnesium hydroxide or aluminum hydroxide and a halogen flame retardant represented by decabromodiphenyl ether is widely known.
[0003]
However, when inorganic flame retardants are used, it is difficult to obtain the desired level of flame retardant effects unless they are blended in an equal amount or more with the target base resin, and the resin's lightness, mechanical strength, price, etc. are only impaired. In addition, problems such as a decrease in fluidity at the time of molding occur. Halogen flame retardant blending can achieve the target level of flame retardancy with a relatively small blending amount, but toxic gases such as dioxins may be generated when the resin composition is discarded or incinerated. In addition to being shunned recently, there is also concern about the problem of corrosion of molding machines due to gas and smoke derived from halogen compounds.
[0004]
For this reason, development of non-halogen flame retardants is underway. For example, JP-A 61-106643 discloses a condensed phosphate compound such as ammonium carbamylpolyphosphate and a triazine compound such as melamine powder. Incorporating a nitrogen-based composite phosphate compound, JP-B-60-35947, JP-A-59-147050, and JP-A-1-193347 disclose ammonium polyphosphate and 1,3,3. A system comprising a 5-triazine derivative is disclosed, and JP-A-60-36542 discloses a composition comprising ammonium polyphosphate and a polyhydroxy low-molecular compound such as pentaerythritol.
[0005]
However, these prior arts are not satisfactory due to the problems of deterioration in physical properties due to the blending of the flame retardant, mold contamination during molding, appearance of the surface of the molded product, and stickiness.
[0006]
In order to improve the water resistance of polyphosphates (for example, ammonium polyphosphate), the degree of polymerization is increased or the surface coating is commercially available, but the water resistance level is still insufficient, and the surface coating The melamine resin often used in No. 1 is not suitable because of its low thermal stability, which causes decomposition during melt kneading of the resin.
[0007]
It is an object of the present invention to provide a flame retardant olefin resin composition and a molded product obtained therefrom, which do not contaminate the mold during molding and do not have a sticky molded product.
[0008]
[Means for Solving the Problems]
As a result of repeated research to improve mold contamination during molding and stickiness of molded products while maintaining excellent flame retardancy, the present inventor has changed to polyphosphoric acid instead of ammonium polyphosphate as a flame retardant component. It has been found that the above-mentioned problems can be solved by using melamine, and furthermore, by setting the NMR peak area ratio of the polymerization degree of the melamine polyphosphate to a predetermined range, it has been found that a more excellent effect can be obtained, and the present invention completed.
[0009]
The present invention contains (A) 100 parts by mass of an olefin resin, (B) 10-60 parts by mass of melamine polyphosphate, and (C) 10-60 parts by mass of a carbonizing agent. Provided is a flame-retardant olefin-based resin composition having a component blending ratio [(B) / (C)] (mass ratio) of 0.5 to 4.5.
[0010]
Further, the present invention comprises (A) 100 parts by mass of an olefin resin, (B) 10-60 parts by mass of melamine polyphosphate, (C) 10-60 parts by mass of a carbonizer, and (D) 1-30 parts by mass of a carbonization accelerator. A flame retardant olefin-based resin composition containing the component (B) and the component (C) in a range of [(B) / (C)] (mass ratio) of 0.5 to 4.5 I will provide a.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The (A) component olefin resin used in the present invention is ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 3-methylbutene-1,4-methylpentene-1. Containing α-olefin homopolymers such as, or random or block copolymers of these α-olefins, or these α-olefins as the main component (preferably 50% by mass or more), and other monomers. Mention may be made of copolymerized copolymers.
[0012]
Examples of other monomers include dienes such as butadiene, isoprene, dicyclopentadiene, 1,4-hexadiene, 4-ethylidene-2-norbornene, dicyclopentadiene, acrylic acid, methacrylic acid, maleic acid, vinyl acetate , Unsaturated acids such as methyl methacrylate and maleic imide or derivatives thereof, aromatic alkenyl compounds such as styrene and α-methylstyrene, and the like, and these can be used alone or in combination.
[0013]
As the component (A), amorphous or crystalline polyolefin can be used, but preferably exhibits crystallinity. Among these, polyethylene, polypropylene, poly (1-butene), ethylene-propylene copolymer, poly (3-methylbutene-1), and poly (4-methylpentene-1) are preferable.
[0014]
The (B) component melamine polyphosphate used in the present invention is melamine or a polyphosphate salt thereof, and includes melamine polyphosphate, melam polyphosphate, and melem polyphosphate.
[0015]
The melamine polyphosphate of the component (B) is an area of a peak a detected at +5 to -5 ppm in a solid-state NMR (measured by DD-MAS method) spectrum using phosphorus of the melamine polyphosphate of the component (B) as an observation nucleus. The ratio of the area of peak b detected at -5 to -17 ppm and the area of peak c detected at -17 to -32 ppm satisfies the following relationships (I) and (II): Is preferred.
[0016]
(I) Area of peak b / area of peak c ≧ 2
(II) Area of peak a / (area of peak b + area of peak c) ≦ 0.1
The area ratio of (I) is more preferably 3 or more, still more preferably 3.5 or more, and the area ratio of (II) is more preferably 0.08 or less, still more preferably 0.05 or less. is there. When the area ratio of (I) and (II) does not satisfy the above numerical range, stickiness of the surface of the molded product when the composition is melt kneaded and molded is large.
[0017]
(B) The compounding quantity of a component is 10-60 mass parts with respect to 100 mass parts of (A) component, Preferably it is 10-50 mass parts, More preferably, it is 10-45 mass parts. When it is 60 parts by mass or less, the mechanical properties of the composition are not deteriorated, and when it is 10 parts by mass or more, formation of a carbonized layer at the time of combustion becomes sufficient and flame retardancy is exhibited.
[0018]
As the carbonizing agent for the component (C) used in the present invention, those selected from pentaerythritol dimer or higher condensates and esters thereof are preferred. Pentaerythritol and esters thereof, dipentaerythritol and esters thereof, 1 or 2 or more chosen from the ester is more preferable.
[0019]
The component (C) contains the above-mentioned pentaerythritol condensate as a main component (preferably 80% by mass or more), and other carbonizers can be blended as the balance.
[0020]
Other carbonization agents include polyols such as pentaerythritol, cellulose, maltose, glucose, arabinose, ethylene glycol, propylene glycol, polyethylene glycol, and ethylene / vinyl alcohol copolymer; or these polyol components react with carboxylic acid. Ester compounds produced; melamine, other melamine derivatives, guanamine or other guanamine derivatives, melamine (2,4,6-triamino-1,3,5-triazine), isocyanuric acid, tris (2-hydroxyethyl) isocyanur Examples thereof include triazine derivatives such as acid, tris (hydroxymethyl) isocyanuric acid, tris (3-hydroxypropyl) isocyanurate, and tris (4-hydroxyphenyl) isocyanurate.
[0021]
The form of the component (C) is not particularly limited, but in the present invention, the average particle size is preferably less than 50 μm, more preferably less than 40 μm, and even more preferably less than 30 μm. .
[0022]
(C) The compounding quantity of a component is 10-60 mass parts with respect to 100 mass parts of (A) component, Preferably it is 15-50 mass parts, More preferably, it is 15-45 mass parts. If it is 60 parts by mass or less, the mechanical strength of the molded product does not decrease or the surface is not sticky, and if it is 10 parts by mass or more, formation of a carbonized layer at the time of combustion becomes sufficient, which is difficult. Flammability is manifested.
[0023]
In the composition of the present invention, the blending ratio (mass ratio) of the component (B) / (C) component is 0.5 to 4.5, preferably 1 to 4, more preferably 1 in order to increase flame retardancy. It is the range of ~ 3.
[0024]
Examples of the carbonization accelerator of component (D) used in the present invention include organometallic complex compounds such as ferrocene, metal hydroxides such as cobalt hydroxide, magnesium hydroxide, and aluminum hydroxide, and boric acids such as magnesium borate and calcium magnesium borate. Alkaline earth metal salts, manganese borate, zinc borate, zinc metaborate, antimony trioxide, alumina trihydrate, nickel oxide, manganese oxide, titanium oxide, silicon oxide, cobalt oxide, zinc oxide and other metal oxides, Aluminosilicates such as zeolite, silicate type solid acids such as silica titania, metal phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate, hydrotalcite, kaolinite, sericite, pyrophyllite And clay minerals such as bentonite and talc.
[0025]
(D) The compounding quantity of a component is 1-30 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.5-10 mass parts, More preferably, it is 0.5-5 mass parts. When the amount is 30 parts by mass or less, the flame retardancy is lowered and the extrusion becomes unstable, and the mechanical properties are not deteriorated.
[0026]
In this invention, other components other than the said (A)-(C) component or (A)-(D) component can be mix | blended as needed.
[0027]
As other components, as a foaming agent, melamine, melamine formaldehyde resin, methylol melamine having 4 to 9 carbon atoms, melamine derivatives such as melamine cyanurate, urea, thiourea, (thio) urea-formaldehyde resin, 2 to 2 carbon atoms 5 from urea derivatives such as methylol (thio) urea, guanamines such as benzoguanamine, phenylguanamine, acetoguanamine, succinylguanamine, reaction products of guanamines with formaldehyde, nitrogen-containing compounds such as dicyandiamide, guanidine and guanidine sulfamate. Mention may be made of what is chosen.
[0028]
Other additives include various phosphate esters such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (o- or p-phenylphenyl) phosphate, trinaphthyl phosphate. , Cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, o-phenylphenyl dicresyl phosphate, tris (2,6-dimethylphenyl) phosphate, tetraphenyl- m-phenylene diphosphate, tetraphenyl-p-phenylene diphosphate, phenyl resorcinol polyphosphate, bisphenol A-bis (diphenyl Phosphate), bisphenol A · polyphenyl phosphate, and di pyrocatechol Hi-Posi phosphate and the like. In addition, as fatty acid / aromatic phosphate ester, diphenyl (2-ethylhexyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, phenylneopentyl phosphate, pentaerythritol diphenyl diphosphate, Mention may be made of orthophosphate esters such as ethylpyrocatechol phosphate and mixtures thereof.
[0029]
You may mix | blend a filler with the composition of this invention according to a use etc. The filler is preferably a fiber, flake, plate, granule or the like that is generally used for reinforcing a thermoplastic resin. As the filler, organic compounds such as glass, carbon, silicon-containing compounds, metal compounds such as potassium titanate, synthetic resins, and cellulose fibers can be used. In the case of inorganic fillers, adhesion to resin components is possible. In order to improve the surface, it is preferable to perform a surface treatment with silane, epoxy, acrylic, titanate coupling agent or the like.
[0030]
The composition of the present invention includes heat, light or oxygen stabilizers (antioxidants such as phenolic compounds and phosphorus compounds, UV absorbers such as benzotriazole compounds, benzophenone compounds and phenyl salicylates, hindered amines) Stabilizers, heat stabilizers such as tin compounds and epoxy compounds), plasticizers, slidability improvers such as polydimethylsiloxane, lubricants, mold release agents, antistatic agents, colorants, and the like can be blended. .
[0031]
The composition of the present invention is kneaded using a melt kneading machine such as a Banbury mixer, open roll, kneader, uniaxial or multi-screw extruder, or mixed with a Henschel mixer, a tumbler mixer, etc., and then kneaded with the melt kneading machine. You can get it.
[0032]
【Example】
The following examples further illustrate the present invention, but the present invention is not limited to these examples.
[0033]
Examples 1-8, Comparative Examples 1-4
Using a Brabender Plasticcoder Mixer (manufactured by Toyo Seiki, Labo Plast Mill 50R150 type), a resin composition was prepared with the formulation shown in Table 1 (in parts by mass). The kneading temperature was 220 ° C., the rotation speed was 50 rpm, and the kneading time was 5 minutes. The resulting composition was press-molded into a 3 mm thick plate and cut to a suitable size for testing. Details of the components used and test methods are as follows.
(1) Component used Component of Example (A) Component Polypropylene: Grand Polypro J713M
(B) Component Melamine polyphosphate-1: Melapur 200 manufactured by DSM. (I) Area ratio = 3.98, (II) Area ratio = 0.04, P content 15%
Melamine polyphosphate-2: Awanon MPP-A from Sanwa Chemical. Area ratio of (I) = 0.7, area ratio of (II) = 0.16, P content is 15%
Component (C) Pentaerythritol dimer: Guangei Chemical's “Dipentolite”
Adipic acid ester of dipentaerythritol: Ajinomoto Fine Techno Plenizer ST210
Tripentaerythritol: Reagent (manufactured by Acros Organics)
Component (D) Zinc borate: U.I. S. “Firebreak ZB” made by Borax
Manganese oxide: Reagent crystalline aluminosilicate manufactured by Kanto Chemical: Molecular sieve 3A (LZY54 manufactured by JGC Universal)
Component of Comparative Example Ammonium Polyphosphate-1: Exolit AP422 from Clariant
Ammonium polyphosphate-2: Taihei S
(2) Test method
(2-1) A vertical combustion test defined in flame retardancy UL-94 was conducted. 6mm wide, 1/8 inch thick (about 3mm)
The sample was held in the flame twice for 10 seconds, and the time until the fire extinguished when the fire was removed was measured each time. The evaluation of V-0 satisfies the following requirements (a) to (e). (A) none of the specimens burns for more than 10 seconds, (b) the total of 10 firing times for each set of five specimens does not exceed 50 seconds, (c) any Neither test specimen burns with combustion reaching the support clamp, (d) Both test specimens drop flame particles that ignite surgical absorbent cotton placed 12 inches below the test specimen. (E) None of the specimens are accompanied by incandescent burning that lasts for more than 30 seconds after the second removal of the test flame.
[0034]
(2-2) Combustion test using corn calorimeter A test piece of 45 × 50 × 3 mm was prepared using the obtained pellet, and 30 kW / m ^{2 was} measured using a corn calorimeter (Corn Calorimeter III, manufactured by Toyo Seiki Co., Ltd.). A combustion test was performed under radiant heat conditions, an instantaneous maximum heat generation rate (kW / m ² ) was measured, and the flame retardancy was evaluated. The lower the maximum heat generation rate, the better the flame retardancy.
[0035]
(2-3) Stickiness of molded product A few drops of water were dropped on the surface of the flat sample immediately after molding, and the presence or absence of stickiness when rubbed by hand was evaluated.
[0036]
○: No stickiness or hardly felt Δ: Some stickiness is felt ×: Very sticky [0037]
[Table 1]

[0038]
In Examples 1 to 7, the flame retardancy was at the V-0 level, and there was no stickiness of the molded product. In Example 8, the flame retardancy was at the V-0 level, but the stickiness of the molded product was large, and there was room for improvement depending on the application. In Comparative Examples 1 and 2, since the ratio of (B) melamine polyphosphate to (C) the carbonizing agent is 5, the flame retardancy is not sufficient, but the stickiness of the molded product is not bad. In Comparative Examples 3 and 4, since ammonium polyphosphate-1 or -2 was blended, the flame retardancy was V-0 level, but the stickiness of the molded product was remarkably high, and the mold contamination during press molding was also severe.
[0039]
【The invention's effect】
According to the composition of the present invention, a molded product having excellent flame retardancy can be obtained, and a molded product with less stickiness can be provided depending on the application.

Claims (8)

  (A) 100 parts by mass of an olefin resin, (B) 10-60 parts by mass of melamine polyphosphate, and (C) one or two or more carbonizing agents selected from pentaerythritol, dipentaerythritol, tripentaerythritol, or esters thereof. A flame-retardant olefin resin composition containing ~ 60 parts by mass, and the blending ratio [(B) / (C)] (mass ratio) of the component (B) and the component (C) is in the range of 1 to 4 object.   (A) 100 parts by mass of an olefin resin, (B) 10 to 60 parts by mass of melamine polyphosphate, (C) one or two or more carbonizing agents selected from pentaerythritol, dipentaerythritol, tripentaerythritol, or esters thereof 60 parts by mass and (D) 1 to 30 parts by mass of a carbonization accelerator, and the blending ratio [(B) / (C)] (mass ratio) of the component (B) and the component (C) is 1 to 1. The flame-retardant olefin resin composition which is the range of 4.   The flame retardant olefin resin composition according to claim 1 or 2, wherein the olefin resin of component (A) is polypropylene. (B) In the solid state NMR (measurement by DD-MAS method) spectrum using phosphorus of melamine polyphosphate as an observation nucleus, the area of peak a detected at +5 to -5 ppm, detected at -5 to -17 ppm The flame retardancy according to any one of claims 1 to 3, wherein the ratio of the area of the peak b and the area of the peak c detected at -17 to -32 ppm satisfies the following relationships (I) and (II): Olefin resin composition.
(I) Area of peak b / area of peak c ≧ 2
(II) Area of peak a / (area of peak b + area of peak c) ≦ 0.1   The flame retardant olefin resin composition according to any one of claims 1 to 4, wherein the component (B) contains melam and / or melem as a counter cation of polyphosphoric acid in addition to melamine. The flame retardant olefin resin according to any one of claims 2 to 5, wherein the carbonization accelerator (D) is one or more selected from zinc borate, manganese oxide, silicon oxide, and aluminosilicate. Composition.   Furthermore, the flame-retardant olefin resin composition of any one of Claims 1-6 containing a filler.   The molded article obtained using the flame-retardant olefin resin composition of any one of Claims 1-7.