JP3133099B2 - Flame-retardant resin composition with good moldability - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyolefin resin,
The present invention relates to a moldable flame-retardant polyolefin resin composition comprising a mixture of an inorganic flame retardant and a higher fatty acid and a fatty acid metal salt. More specifically, the present invention relates to a flame-retardant polyolefin-based resin composition which does not generate harmful gases, has a high degree of flame retardancy, and does not generate resin deposits even when continuously molded. .

[0002]

2. Description of the Related Art Conventionally, polyvinyl chloride resin (PVC) has been used as a flame-retardant resin composition used for covering electric wires and cables.
There is known a flame-retardant sheet in which a crosslinked PVC having abrasion resistance and / or heat resistance is provided on a substrate made of C). However, although the above PVC has flame retardancy,
PVC is heavy and has problems such as toxicity due to residual vinyl chloride monomer and plasticizer, and not only loss of flexibility when used for many years, but also generation of toxic gas during combustion. In recent years, there has been a demand for a material that does not have the toxicity problem of replacing PVC, is lightweight, and can be used stably for a long period of time. The use of a polyolefin in place of the above PVC can reduce the weight. However, the use of a polyolefin alone is flammable, and the use of a resin composition containing an organic flame retardant such as a halogen-based flame retardant in the polyolefin reduces the weight. Although flame retardancy can be achieved, organic flame retardants such as halogen-based flame retardants have the problem of generating toxic gases during combustion, similar to PVC. In recent years, polyolefins do not generate harmful gases, have low smoke, and are pollution-free flame retardants.
It has been proposed to add an inorganic flame retardant such as aluminum hydroxide and magnesium hydroxide (see, for example,
1-1132254, JP-A-56-136832, JP-A-1-234436, etc.). However, if a large amount of the inorganic flame retardant is mixed with the polyolefin, a continuous operation for a long time generates resin deposits (eyes) at the exits of dies and nozzles, roughening or damaging the surface of the molded product, or depositing the resin. There is a problem in that the product is oxidatively degraded, so-called burnt resin is generated, and defective products are generated or the quality of the product is significantly reduced.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above points, and has been made in earnest by using a halogen-free, non-polluting, highly flame-retardant composition,
Even when driving for a long time, eyes and eyes do not occur,
An object of the present invention is to provide a flame-retardant resin composition capable of obtaining a molded article having excellent surface appearance having excellent flexibility, mechanical properties, electrical properties and the like.

[0004]

The first aspect of the present invention SUMMARY OF] is the (A) polyolefin resin relative to the total weight of the polyolefin-based resin (A1) and the following Poriore fins resin (A2) (A2) 0 0.02 to 10% by weight of a resin composition containing 2 to 10% by weight; (B) 30 to 200 parts by weight of an inorganic flame retardant; (C) a mixture of a higher fatty acid and (D) a divalent or higher-valent metal fatty acid salt; It is a flame-retardant resin composition having good moldability which does not generate resin deposits (even eyes) even when continuously molded containing 5 parts by weight. Polyolefin-based resin (A2): a1: carboxylic acid group, carboxylic acid ester group or acid anhydride group-containing monomer, a2: epoxy group-containing monomer, a
3: Hydroxyl group-containing monomer, a4: Amino group-containing monomer, a5: Alkenyl cyclic imino ether derivative, a6: Polyfunctional monomer, a7: Unsaturated organic titanate compound, a8: At least one selected from unsaturated organic silane compounds 0.01 to 20% by weight of the reactive compound
Graft-modified polyolefin resin The second invention of the present invention relates to the flame-retardant resin composition having good moldability according to claim 1, wherein the polyolefin resin (A1)
Is a polyolefin resin selected from ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, and ultra-low density polyethylene, and the polyolefin resin (A2) is a carboxylic acid group, a carboxylic ester group or an acid anhydride group. It is a polyolefin resin obtained by graft-modifying the contained monomer. According to a third aspect of the present invention, there is provided a flame-retardant resin composition having good moldability according to the first or second aspect, wherein the polyolefin-based resin (A1) is used.
And a resin composition comprising a polyolefin resin (A2), (B) an inorganic flame retardant, (C) a higher fatty acid, and (D) 2
It is characterized by comprising a mixture with a metal fatty acid salt having a valency or higher, a pigment, an anti-scratching whitening agent, an antioxidant and an ultraviolet absorber. A fourth invention of the present invention is the flame-retardant resin composition having good moldability according to any one of the first to third aspects, wherein the metal fatty acid salt is calcium stearate.

The polyolefin resin (A1) which is the component (A) of the present invention includes ultra-low density polyethylene, high pressure low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-propylene Olefin rubbers such as copolymer rubber, ethylene-propylene-diene copolymer rubber, ethylene-butene-1 copolymer rubber, ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymer, ethylene-
Ethylene-based (co) polymers such as copolymers with ethylene-α, β-carboxylic acids or derivatives thereof, such as alkyl (meth) acrylate copolymers, polypropylene,
Examples include a polypropylene-based polymer such as a propylene-ethylene copolymer and a polybutene-based polymer. Among these, ethylene (co) polymers having a density of 0.86 to 0.94 g / cm ³ , such as very low density polyethylene (VLDPE), high pressure method low density polyethylene (LDPE), and linear low density polyethylene (LLDPE); Olefinic rubbers such as propylene copolymer rubber (EPR), ethylene-propylene-diene copolymer rubber (EPDM) and ethylene-butene-1 copolymer rubber, and ethylene such as ethylene-vinyl acetate copolymer (EVA) Soft polyolefin-based polymers such as copolymers with ethylene-α, β-carboxylic acid or derivatives thereof, such as vinyl ester copolymers, ethylene-alkyl (meth) acrylate copolymers, and the like; Such a composition or mixture is preferred from the viewpoint of acceptability and compatibility of the flame retardant, the filler, and the like.

The very low density polyethylene (VLDPE)
The term “polyethylene” refers to polyethylene having a density of 0.86 to 0.910 g / cm ³ and having properties intermediate between linear low-density polyethylene and ethylene-α-olefin copolymer rubber. For example, a density of 0.860 to 0.910 g / cm ³ and a differential scanning calorimetry (DS
C) a specific ethylene-α-olefin copolymer having a property of having a maximum peak temperature (Tm) of 60 ° C. or more and preferably a boiling n-hexane insoluble content of 10% by weight or more, wherein at least titanium and / or vanadium are used. Resin polymerized using a catalyst comprising a solid catalyst component and an organoaluminum compound and having both a high crystalline portion represented by linear low density polyethylene and an amorphous portion represented by ethylene-α-olefin copolymer rubber However, the former feature of mechanical strength, heat resistance and the like, the latter feature of rubber-like elasticity, low-temperature impact resistance and the like coexist in a well-balanced manner, and are extremely useful when used in the present invention. . The α-
Examples of the olefin include propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, and dodecene-1.

[0007] As the olefin rubber of the present invention, ethylene-propylene-diene random copolymer rubber and ethylene-propylene random copolymer rubber are particularly preferred. These two rubbers are superior in thermoplasticity to other rubbery substances, are easily dispersed by melt kneading, and
Compared with R, isoprene rubber, nitrile rubber, butadiene rubber, etc., it has no peculiar odor, or it can be obtained in pellet form, so it is easy to measure and handle when compounding, and the type of composition manufacturing equipment Also has operational advantages such as a large degree of freedom in selection. With respect to the diene component of the ethylene-propylene-diene random copolymer rubber, ethylidene norbornene, dicyclopentadiene, 1,4-
Any of cyclohexadiene and the like can be used. The Mooney viscosity (ML1 + 4 100 ° C.) of these rubbery substances is 10
-100, preferably (ML1 + 4100 ° C) 20-90. When the Mooney viscosity (ML1 + 4 100 ° C.) is 10 or less, the effect of improving the impact resistance is hardly obtained. There is a fear that the dispersion with the flame retardant becomes worse.

The propylene-based or butene-based soft polyolefin of the present invention is a propylene-α-olefin random copolymer or a butene-1-α-olefin random copolymer produced using a Ziegler-based catalyst, and has a low crystallinity. Or non-crystalline polyolefin.

Furthermore, in the present invention, isobutene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene random copolymer rubber, chloroprene rubber, nitrile rubber, styrene-butadiene-styrene block copolymer rubber, styrene- It may be used by adding isoprene-styrene block copolymer rubber or the like.

[0010] The ethylene-vinyl ester copolymer of the present invention comprises ethylene produced by a high-pressure radical polymerization method, comprising ethylene as a main component, vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, stearic acid. It is a copolymer with vinyl ester monomers such as vinyl and vinyl trifluoroacetate. Among them, particularly preferred is vinyl acetate. That is, a copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of a vinyl ester, and 0 to 49.5% by weight of another copolymerizable unsaturated monomer is preferable.

The copolymer of the present invention with an ethylene-α, β-unsaturated carboxylic acid or a derivative thereof includes ethylene-α, β-unsaturated carboxylic acid copolymer and ethylene-α, β-unsaturated carboxylic acid copolymer.
β-unsaturated carboxylic acid ester copolymers, metal salts thereof, amides, imides, etc., are preferred. Ethylene produced by a high-pressure radical polymerization method is preferably 50 to 99.5% by weight, and α, β-unsaturated. Carboxylic acid or ester
Copolymers consisting of 5 to 50% by weight and 0 to 49.5% by weight of other copolymerizable unsaturated monomers are preferred.

Specific examples of the above α, β-unsaturated carboxylic acids or esters include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, and acrylic acid. Methyl acid,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate,
Isopropyl acrylate, isopropyl methacrylate,
N-butyl acrylate, n-butyl methacrylate,
Cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, monomethyl maleate, monoethyl maleate, diethyl maleate, monomethyl fumarate, glycidyl acrylate, methacryl And unsaturated carboxylic esters such as glycidyl acid. Of these, alkyl (meth) acrylate is particularly preferred. More preferably, ethyl acrylate can be mentioned.

The metal salt includes sodium salt, potassium salt, calcium salt, lithium salt, aluminum salt, magnesium salt, zinc salt and the like.

Specific examples of the above copolymer include ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid-ethyl acrylate copolymer , Ethylene-
Vinyl acetate copolymer, ethylene-vinyl acetate-ethyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-ethyl acrylate copolymer, and metal salts (ionomers) thereof. No. These copolymers may be used as a mixture. In particular, an oxygen-containing soft polyolefin resin such as an ethylene-vinyl ester copolymer or a copolymer with ethylene-α, β-carboxylic acid or a derivative thereof is preferable because of its remarkable flame-retardant synergistic effect. The reason why the oxygen-containing soft polyolefin resin exhibits high flame retardancy when an inorganic flame retardant is blended is not clear, but it is considered to be due to a synergistic effect with the inorganic flame retardant during combustion.

The polyolefin resin composition containing the reactive compound of the present invention includes: a1: a carboxylic acid group, a carboxylic ester group or an acid anhydride group-containing monomer, a2: an epoxy group-containing monomer, a3: a hydroxyl group-containing monomer, a4: amino group-containing monomer, e: alkenyl cyclic imino ether derivative, a5: polyfunctional monomer, a7: unsaturated organic titanate compound, a8: polyolefin containing at least one reactive group selected from unsaturated organic silane compounds Resin (A2) or its resin composition 100
It comprises a resin composition containing parts by weight and 30 to 200 parts by weight of an inorganic flame retardant (B).

The polyolefin-based resin containing a reactive group of the present invention is a binary or multi-component copolymer of an olefin and at least one of the above-mentioned monomers, or a graft-modified polyolefin-based resin obtained by graft-modifying at least one of the monomers. Modified products, which include thermoplastic resin compositions in which at least one of the monomers is impregnated in a polyolefin resin, are graft-modified products because the operation is simple, effective, and inexpensive. Is most preferred.

The above-mentioned reactive group a1: carboxylic acid group, carboxylic acid ester group or acid anhydride group-containing monomer includes α, such as maleic acid, fumaric acid, citraconic acid and itaconic acid.
β-unsaturated dicarboxylic acid, acrylic acid, methacrylic acid,
Examples include unsaturated monocarboxylic acids such as furanic acid, crotonic acid, vinyl acetic acid, and pentenoic acid, and esters or anhydrides of these α, β-unsaturated dicarboxylic acids or unsaturated monocarboxylic acids.

A2: As the epoxy group-containing monomer,
Glycidyl acrylate, glycidyl methacrylate, monoglycidyl ester of itaconic acid, monoglycidyl ester of butenetricarboxylic acid, diglycidyl ester of butenetricarboxylic acid, triglycidyl ester of butenetricarboxylic acid and α-chloroallyl, maleic acid, crotonic acid, fumaric acid, etc. Glycidyl esters or vinyl glycidyl ether, allyl glycidyl ether, glycidyloxyethyl vinyl ether, styrene-p-
Glycidyl ethers such as glycidyl ether, p-
Glycidyl styrene and the like can be mentioned, and particularly preferred are glycidyl methacrylate and allyl glycidyl ether.

A3: As the hydroxyl group-containing monomer, 1-hydroxypropyl (meth) acrylate, 2
-Hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate and the like.

A4: Examples of the amino group-containing monomer include tertiary amino group-containing monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dibutylaminoethyl (meth) acrylate.

A5: The alkenyl cyclic imino ether derivative is represented by the following structural formula (Formula 1):

Embedded image [Where n is 1, 2 and 3, preferably 2 and 3, more preferably 2. R ¹ , R ² , R ³ ,
R represents a C1 to C12 inactive alkyl group and / or hydrogen, and each of the alkyl groups may have an inactive substituent.] The term "inert" as used herein refers to the function of the graft reaction or its product. Does not adversely affect Also, R need not all be the same. Preferably R ¹ ＲR ² ＨH, R ³ ＨH or Me, RＲH, ie 2-vinyl and / or 2-isopropenyl-2-
Oxazoline, 2-vinyl and / or 2-isopropenyl-5,6-dihydro-4H-1,3-oxazine. These may be used alone or as a mixture. Among them, 2-vinyl and / or 2-isopropenyl-2-oxazoline are particularly preferred.

A6: Polyfunctional monomers include polyfunctional methacrylate monomers represented by trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc., divinylbenzene, triallyl isocyanurate,
Polyfunctional vinyl monomers represented by diallyl phthalate, vinyl butyrate, etc., bismaleimides represented by N, N'-m-phenylene bismaleimide, N, N'-ethylene bismaleimide, P-quinone dioxime Dioximes and the like.

A7: Examples of the unsaturated titanate compound include tetraisopropyl titanate, tetra-n-butyl titanate, tetrakis (2-ethylhexoxy) titanate, and titanium lactate ammonium salt.

A8: Examples of the unsaturated silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetylsilane, vinyltrichlorosilane and the like.

When at least one of the above monomers is graft-modified to a polyolefin resin, it is desirable to carry out the grafting in the presence of a crosslinking agent without a solvent or in a solvent. Examples of the crosslinking agent include hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester,
At least one selected from organic peroxides such as ketone peroxides, dihydroaromatic compounds, and vulcanizing agents such as sulfur is included.

The polyolefin resin to be graft-modified is not particularly limited. For example, in the case of a composition in which the polyolefin-based resin containing the reactive group alone is blended with an inorganic flame retardant, it is preferable that the polyolefin-based resin containing the reactive group is essentially a soft polyolefin-based resin. . Further, when a resin composition blended with a polyolefin resin containing a reactive group and another soft polyolefin resin and an inorganic flame retardant are blended, the polyolefin resin containing a reactive group is not necessarily a soft polyolefin resin. It is not necessary to be composed of a resin having high crystallinity, such as high-medium density polyethylene and polypropylene.
0.97 g / cm ^{3 of} an ethylene-α-olefin copolymer is preferably used.

The amount of the reaction or grafting of the reactive group is as follows:
It is used in an amount of 0.01 to 20% by weight, preferably 0.1 to 15% by weight, based on the resin component. The soft polyolefin resin to be modified according to the present invention or the soft polyolefin resin blended with the polyolefin resin containing a reactive group is appropriately selected from at least one of the polyolefin resins (A1).

The inorganic flame retardant of the component (B) of the present invention includes aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, basic magnesium carbonate, dolomite,
Hydrotalcite, calcium hydroxide, barium hydroxide, hydrate of tin oxide, hydrate of inorganic metal compounds such as borax, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium-calcium carbonate, Examples include calcium carbonate, barium carbonate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, antimony oxide, and red phosphorus. These may be used alone or in combination of two or more. Among them, in particular, at least one selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, and hydrotalcite
The seed has good flame retardant effect and is economically advantageous.

In order to promote char (carbonized layer), at least one of inorganic metal hydrates such as aluminum hydroxide and magnesium hydroxide and at least one of red phosphorus or phenolic resin-coated red phosphorus, carbon black, borate, etc. It is preferable to use it in combination with a seed. It is desirable to add the char forming aid such as red phosphorus in an amount of about 0.5 to 20% by weight with respect to the inorganic flame retardant. Although the particle size of these inorganic flame retardants differs depending on the type, the average particle size of magnesium hydroxide, aluminum hydroxide and the like is 20%.
μm or less is preferred.

The amount of the inorganic flame retardant is 10
30 to 200 parts by weight, preferably 50 to 0 parts by weight
It is in the range of 150 parts by weight. If the amount of the flame retardant is less than 30 parts by weight, the combustion effect is small, and if it exceeds 200 parts by weight, the mechanical strength and elongation are reduced, the flexibility is lost, the material becomes brittle, and the low-temperature properties are deteriorated.

The higher fatty acid of the component (C) of the present invention includes natural or synthetic saturated or unsaturated fatty acids such as palmitic acid, stearic acid, oleic acid and lauric acid, and usually has about 10 to 24 carbon atoms. It is a higher fatty acid. Examples of the (D) divalent or higher-valent fatty acid metal salt include calcium salts, aluminum salts, magnesium salts, and zinc salts of the above-mentioned higher fatty acids. In the present invention, it is important that the mixture is a mixture of the above higher fatty acid and a metal salt of a divalent or higher fatty acid. The mixture ratio of the mixture is higher fatty acid / fatty acid metal salt = 10-90 / 90-10, preferably 30-70 / 70-30, more preferably 40-90.
It is in the range of 60/60 to 40. When the higher fatty acid or the fatty acid metal salt is lacking, it is not possible to prevent the eyes generated during long-term operation. The amount of the mixture is 100 parts by weight of polyolefin resin, 3 parts of inorganic flame retardant,
It is 0.01 to 5 parts by weight based on 0 to 200 parts by weight. If the amount is less than 0.01, the effect may not be exhibited. If the amount is more than 5 parts by weight, not only may a slip phenomenon occur in the extruder, but also bleed out on the surface of the molded product. However, there is a possibility that the appearance of the product may be impaired.

In the present invention, by using an inorganic filler and a flame retardant in combination, the amount of the flame retardant added can be reduced, and other characteristics can be imparted. As the inorganic filler used in the present invention, powder, granular, flat,
Needle, spherical or hollow and fibrous and the like, specifically, calcium carbonate, magnesium carbonate, calcium sulfate, calcium silicate, clay, diatomaceous earth, talc,
Granular fillers such as alumina, silica sand, glass powder, iron oxide, metal powder, antimony trioxide, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black, mica, glass plate, sericite, Metallic foils such as pyrophyllite and aluminum flakes, flat or flaky fillers such as graphite, hollow fillers such as shirasu balloons, pumice stones, glass fibers, carbon fibers, graphite fibers, whiskers, metal fibers, silicone carbide Examples include fibers, mineral fibers such as asbestos and wollastonite.

These addition amounts are applied up to about 100 parts by weight with respect to 100 parts by weight of the resin component. If the amount exceeds 100 parts by weight, the mechanical strength such as the impact strength of the composition is undesirably reduced.

An anti-scratching whitening agent may be added to the resin composition used in the present invention as long as its properties are not impaired. Examples of the whitening inhibitor include mineral oils, waxes, paraffins, other higher fatty acids and their esters, amides or metal salts, silicones, partial fatty acid esters of polyhydric alcohols or fatty alcohols, fatty acids, fatty acid amino, fatty acid amides. , Alkyl phenol or alkyl naphthol alkylene oxide adduct. Among the above-mentioned anti-scratch whitening agents, silicones such as oleic acid amide, stearic acid amide, higher fatty acid amide and higher fatty acid-modified silicone oil are preferable, and higher fatty acid amide is economically advantageous because it is inexpensive.

In the present invention, an organic filler, an antioxidant, a lubricant, an organic or inorganic pigment, an ultraviolet ray inhibitor, a dispersant, a cross-linking agent within a range that does not impair the physical properties of the resin composition and according to the purpose of use. , A copper damage inhibitor, a neutralizing agent, a plasticizer, a nucleating agent, and the like.

The composition of the present invention generally comprises, first, a polyolefin resin containing a reactive group, an inorganic flame retardant, a metal salt of a higher fatty acid, and if necessary, an inorganic filler, an additive and the like. These are manufactured by dry blending with a normal tumbler, etc., or by melt-kneading with a conventional kneading machine such as a Banbury mixer, pressure kneader, kneading extruder, twin-screw extruder, roll, etc., and uniformly dispersing them. Is done.

The present invention includes the following embodiments. (1) The polyolefin resin (A1) is an ultra-low-density polyethylene, ethylene-vinyl ester copolymer, ethylene-α, β-unsaturated carboxylic acid or its ester copolymer and its metal salt, olefin rubber, propylene The flame-retardant resin composition according to claim 1, wherein the composition is at least one selected from the group consisting of-an ethylene random copolymer and a propylene-butene-1 random copolymer. (2) The flame-retardant resin composition according to claim 1 or 2, wherein the inorganic flame retardant is a hydrate of an inorganic metal compound. (3) The flame-retardant resin composition according to claim 1 or 2, wherein the hydrate of the inorganic metal compound is magnesium hydroxide and / or aluminum hydroxide.

[0038]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but it should not be construed that the invention is limited thereto without departing from the gist of the present invention. [Resin and Material Used] (A1) Component Polyolefin resin: A1-1: Ethylene-ethyl acrylate copolymer (EE
A) [EA content = 15% by weight, MFR = 0.75 g / 10
min. Trade name; Nisseki Lexlon A1150, manufactured by Nippon Petrochemical Co., Ltd.] A1-2: Ethylene-vinyl acetate copolymer (EVA) [VA content = 15% by weight, MFR = 1.5 g / 10 mi]
n. Trade name; Nisseki Lexlon V270, manufactured by Nippon Petrochemical Co., Ltd.] A1-3: Very low density polyethylene (VLDPE) [density = 0.900 g / cm ³ , MFR = 0.5 g / 10 mi]
n. Product name: Nisseki Softlex D9005, manufactured by Nippon Petrochemical Co., Ltd.]

Component (A2) Polyolefin resin containing a reactive compound: a1: Maleic anhydride-modified linear low-density polyethylene (MAnLLDPE) [density = 0.92 g / cm ³ , MFR = 1.0 g / 10 mi]
n.] a5: Alkenyl cyclic imino ether-modified linear low-density polyethylene (B) component Inorganic flame retardant: B1: magnesium hydroxide [trade name; Kisuma 5BG manufactured by Kyowa Chemical Co., Ltd.] B2: aluminum hydroxide [trade name] ; Heidilight H3
2TX, manufactured by Showa Light Metal Co., Ltd.) (C) Component Higher fatty acid C1: Stearic acid C2: Oleic acid (D) Component Divalent or higher fatty acid metal salt D1: Calcium stearate D2: Zinc stearate The test results are shown in Table 1. .

[0040]

[Table 1]

[Test method] (1) Tensile strength (UTS) and elongation (%) A test piece punched out from a sample having a thickness of 1 mm with a No. 3 dumbbell was measured at a tensile speed of 200 mm / min using Tensilon. . (2) Oxygen index (O.I.) This was performed in accordance with JIS K7201. (3) Occurrence of streaks Hole diameter 2mm, land length 10m by 40mmφ extruder
Using a die having 6 m holes and 6 holes, extrusion was performed for 1 hour at a set temperature of 220 ° C. and an extrusion rate of 16 kg / HR. Eyes generated at that time were sampled and weighed.

[0042]

As described above, the present invention provides a resin composition comprising a polyolefin resin, an inorganic flame retardant, a mixture of a higher fatty acid and a metal salt of a divalent or higher fatty acid,
Formability is significantly improved. In particular, when using such a halogen-free, non-polluting, highly flame-retardant composition and operating for a long period of time, the eyes do not appear, and flexibility, mechanical properties, electrical properties, etc. A molded article having an excellent surface appearance can be obtained. Furthermore, by coupling a polyolefin resin having a specific reactive group with an inorganic flame retardant, dripping does not occur during combustion, and workability, flexibility, mechanical properties, electrical properties, etc. are dramatically improved. It is presumed that it was possible to provide a halogen-free, non-polluting, high level of flame retardancy without any safety problems. The flame-retardant resin composition of the present invention having such excellent properties includes automobiles, vehicles such as trains and buses, ships, aircraft, general houses, and nuclear power laboratories that regulate the amount of corrosive gas. It can be used in places where high flame retardancy is required, such as in various power plants, chemical, steel, petroleum and other plants, and in the fields of textiles, electricity, electronics, construction, civil engineering, and the like.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ identification code FI (C08L 23/00 23:26) (58) Investigated field (Int.Cl. ⁷ , DB name) C08L 23/00-23 / 36 C08K 3/00-3/40 C08K 5/00-5/59 H01B 3/44 H01B 7/295

Claims (4)

(57) [Claims] (A) a polyolefin resin (A1);
Based on the total amount of the following polyolefin resin (A2)
100 parts by weight of a resin composition containing 0.02 to 10% by weight of a polyolefin resin (A2); 30 to 200 parts by weight of (B) an inorganic flame retardant; (C) a higher fatty acid and (D) a divalent or higher metal fatty acid salt. A flame-retardant resin composition having good moldability that does not generate resin deposits (even in the case of continuous molding) containing 0.01 to 5 parts by weight of a mixture of Polyolefin-based resin (A2): a1: carboxylic acid group, carboxylic acid ester group or acid anhydride group-containing monomer, a2: epoxy group-containing monomer, a
3: Hydroxyl group-containing monomer, a4: Amino group-containing monomer, a5: Alkenyl cyclic imino ether derivative, a6: Polyfunctional monomer, a7: Unsaturated organic titanate compound, a8: At least one selected from unsaturated organic silane compounds 0.01 to 20% by weight of the reactive compound
Graft-modified polyolefin resin 2. The polyolefin resin (A1) is a polyolefin resin selected from ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer and ultra-low density polyethylene, and the polyolefin resin (A2) is The flame-retardant resin composition having good moldability according to claim 1, which is a polyolefin-based resin obtained by graft-modifying an acid group, a carboxylic acid ester group or an acid anhydride group-containing monomer. 3. A resin composition comprising a polyolefin resin (A1) and a polyolefin resin (A2),
The composition according to claim 1, comprising (B) an inorganic flame retardant, (C) a mixture of a higher fatty acid and (D) a divalent or higher-valent metal fatty acid salt, a pigment, an anti-whitening agent, an antioxidant and an ultraviolet absorber. The flame-retardant resin composition according to claim 2 having good moldability. 4. The flame-retardant resin composition according to claim 1, wherein the metal fatty acid salt is calcium stearate.