JP2003138072A - Flame-retardant resin composition and resin composite material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a halogen-free and phosphorus-free flame-retardant resin composition which can be produced by using a general-purpose mixing machine without using a specific kneading apparatus on a specific kneading method, excels in moldability and mechanical properties and, simultaneously, excels in flame retardance at a relatively low ratio of the content of a flame-retardant, and a resin composite material using the same. SOLUTION: The flame-retardant resin composition is obtained by finely dispersing an organic salt-treated layered clay mineral into a resin containing a copolymer of ethylene and a polar monomer with the use of a general-purpose mixing machine. The resin composite material is obtained by further mixing the flame-retardant resin composition with other resins.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition which is particularly preferably used for reducing toxic gases such as dioxins generated when various synthetic resin products are burned.

Further, by mixing the flame-retardant resin composition with another resin, the flame-retardant property of the other resin is improved, and at the same time, the flame-retardant property as a resin reinforcing agent such as improvement of elastic modulus and improvement of thermal decomposition temperature. The present invention relates to a resin composite material containing a resin composition.

[0003]

2. Description of the Related Art In recent years, there has been a demand for a technology for suppressing toxic gases such as dioxins generated when various synthetic resin products are burned. In order to suppress the generation of dioxins and the like, a method that does not use a halogen-based flame retardant or a phosphorus-based flame retardant that has been conventionally mixed with a resin is most effective. As such a method, a method using a non-halogen phosphorus-free flame retardant that does not use phosphorus or halogen, which is represented by hydrated metal compounds such as aluminum hydroxide and magnesium hydroxide, is generally used.

However, in order for the non-halogen phosphorus-free flame retardant composed of these hydrated metal compounds to obtain flame retardancy equivalent to that of halogen-based and phosphorus-based flame retardants, the ratio of the resin is 2 to 3 times the flame retardant amount. It should be doubled. Therefore, it is known that the resin composition containing a non-halogen phosphorus-free flame retardant has a relatively high ratio of the flame retardant, and thus is significantly inferior in mechanical properties.

On the other hand, layered clay minerals are disclosed, for example, in Japanese Patent Laid-Open No. 2002-2.
It is used as a gas barrier film as disclosed in Japanese Patent No. 10857. That is, the layered clay compound is
It is known that since the particles have a large aspect ratio, they have a large oxygen barrier performance and an excellent gas barrier performance.

Therefore, it is considered that the flame retardancy of the resin is caused by the oxygen barrier performance. However, as a matter of fact, Japanese Patent Laid-Open No. 11-228
As described in Japanese Patent No. 748, it is the current situation that phosphorus is inserted between layers of a layered clay compound and that flame retardancy is exhibited by the combined use with other compounding agents. It is considered that the flame retardancy becomes insufficient because the fine dispersion and orientation of the layered clay compound in the polymer cannot be controlled, and the ability as a flame retardant aid such as other compounding agents is required. To be

[0007]

On the other hand, in order to reduce the amount of the non-halogen phosphorus-free flame retardant added as much as possible, a flame retardant auxiliary such as tin or silicone is used in combination.
Measures have been taken to reduce the proportion of non-halogen phosphorus-free flame retardants and ensure excellent mechanical properties. However, there is a limit even if the ratio of non-halogen phosphorus-free flame retardant is reduced, and it is not a fundamental measure for securing mechanical properties.

On the other hand, conventionally, addition and mixing of clay have been studied in order to improve the mechanical properties of organic polymer materials. For example, there is a method of dispersing clay in a thermosetting polymer such as nylon, vinyl polymer, epoxy, or rubber (Japanese Patent Laid-Open No. 62-74957, Japanese Laid-Open Patent Publication No. 1-74957).
-198645, G.E. P. Giannelis et al Chem. Mater. 5,1694-1696 (19
93) etc.). These are methods of organizing clay with organic onium ions and initiating polymerization of monomers between clay layers,
A method of incorporating clay into growing seeds, or a method of kneading clay with a polymer to insert a polymer between layers, etc. However, the clay and the polymer are general-purpose extruders (general-purpose mixers).
Sufficient mechanical strength cannot be obtained only by kneading with, so it is the current situation that mechanical strength is obtained by a special kneading device or kneading method, and there is a problem that the manufacturing cost increases. .

Further, the moldability and the obtainability of the resin composite material depend on the fact that the clay is cleaved into each of the silicate plates constituting the clay and the arrangement state of the cleaved silicate plates in the composite material. It is extremely important to improve the physical properties of the obtained molded product. However, until now, the degree of cleavage has not necessarily been discussed, and the problems at the time of molding and the manifestation of the maximum effect on the physical properties and performance of the molded body have not always been sufficient.

The present invention has been made in view of the above circumstances, and is a hybrid body of a clay and a polymer compound produced by a general-purpose mixer without using a special kneading device or a kneading method. Therefore, it is an object of the present invention to provide a non-halogen phosphorus-free flame-retardant resin composition which is excellent in processability and mechanical properties, and which has a relatively low flame retardant content and excellent flame retardancy.

Further, the cleavability of the nanofiller used (for example, an organic silicate plate obtained by subjecting a clay mineral to an organic salt treatment and cleaved) is limited to a certain level or more, and the orientation direction of the filler in the matrix resin is limited. The purpose of this is to provide a flame-retardant resin composition in which the degree of fine dispersion is controlled and the maximum effect as a nanocomposite is exhibited.

Furthermore, by mixing the flame-retardant resin composition with another resin, the flame-retardant property of the other resin is improved, the elastic modulus is improved, and the thermal decomposition temperature is improved. TECHNICAL FIELD The present invention relates to a resin composite material containing a resin composition as a resin reinforcing agent.

[0013]

Means for Solving the Problems The inventors of the present application have made extensive studies in order to achieve the above object. As a result, it was found that the above object can be achieved by finely dispersing an organic salt-treated layered clay mineral in a resin containing a copolymer of ethylene and a polar monomer to obtain high flame retardancy, and completed the present invention. Came to do.

In order to solve the above-mentioned problems, the flame-retardant resin composition of claim 1 is obtained by finely dispersing an organic salt-treated layered clay mineral in a resin containing a copolymer of ethylene and a polar monomer. It is characterized by that.

According to the above constitution, the layered clay mineral treated with the organic salt is finely dispersed in the resin containing the copolymer of ethylene and the polar monomer, that is, uniformly dispersed, so that flame retardancy appears. To do. This makes it possible to effectively provide a flame-retardant resin composition having high flame retardancy by using a relatively low proportion of non-halogen phosphorus-free flame retardant. Further, by uniformly dispersing the layered clay mineral treated with an organic salt using a general-purpose extruder in a copolymer of ethylene and a polar monomer, it is possible to reduce the cost of the production process. Further, the flame-retardant resin composition can improve mechanical properties by uniformly dispersing the organic salt-treated layered clay mineral in a resin containing a copolymer of ethylene and a polar monomer.

In order to solve the above-mentioned problems, the flame-retardant resin composition according to claim 2 has a diffraction angle (2θ (0)) corresponding to that of an organic salt-untreated layered clay mineral by X-ray diffraction. The diffraction intensity (I (0)) is compared with the diffraction intensity (I (1)) of the organic salt-treated layered clay mineral finely dispersed in the resin, and I (1) / I (0) is 0. It is characterized in that the organic salt-treated layered clay mineral is finely dispersed in the resin within a range of 0.75 or less.

According to the above configuration, I (1) / I (0) is 0.7
When it is 5 or less, the cleavage of the layered clay mineral into each sheet becomes more complete and the uncleavable material can be further reduced, so that the moldability and the physical properties and performance of the obtained molded article are improved. .

In order to solve the above-mentioned problems, the flame-retardant resin composition according to a third aspect of the present invention comprises an organic salt-treated layered clay mineral,
It is characterized in that 0.1 to 100 parts by weight is contained with respect to 100 parts by weight of a copolymer of ethylene and a polar monomer.

In order to solve the above-mentioned problems, the flame-retardant resin composition of claim 4 has an oxygen index of 25 or more specified by JIS K 7201 in addition to the constitutions of claims 1-3. Is characterized by.

In order to solve the above problems, the flame-retardant resin composition according to claim 5 has a maximum calorific value of a flame-retardant resin composition containing an organic salt-treated layered clay mineral defined in ASTM E 1354. Is less than three-quarters of the maximum heat value of the resin alone specified in ASTM E 1354.

According to the above constitution, the organic salt-treated layered clay mineral is contained in the resin containing the copolymer of ethylene and the polar monomer and the modified resin composition thereof in the above-mentioned predetermined ratio. Thereby, the flame retardancy can be further improved when the resin composition is burned.

In order to solve the above problems, the flame-retardant resin composition of claim 6 is characterized in that the copolymer is an ethylene-vinyl acetate copolymer.

According to the above constitution, the flame retardancy can be further improved by using the ethylene-vinyl acetate copolymer.

The flame-retardant resin composition of claim 7 is characterized in that the copolymer is modified in order to solve the above problems.

According to the above constitution, since the copolymer is modified, the layered clay mineral treated with the organic salt can be almost completely dispersed in the resin containing the copolymer. More excellent flame retardancy can be obtained. With this, high flame retardancy can be obtained with a smaller amount, and thus more excellent mechanical properties can also be obtained.

In order to solve the above problems, the flame-retardant resin composition according to claim 8 is a sheet in which at least 1/2 of the organic salt-treated layered clay mineral is arranged in parallel with the sheet surface or the film surface. It is characterized in that it is in the form of a film or film.

In order to solve the above-mentioned problems, the flame-retardant resin composition according to claim 9 is a fibrous material in which at least 1/2 of the organic salt-treated layered clay mineral is arranged in parallel with the fiber or rod side surface. It is characterized by being an object or a rod-shaped (cylindrical) object.

According to the above construction, in the case of a one-dimensional molded body having a fibrous or rod-like (cylindrical) shape, it is better to arrange the plates one-dimensionally in the length direction to improve the strength in that direction. In that sense, it is preferable. By arranging in this way, the bending strength and elasticity or the tensile strength and elasticity of the fiber or rod-like material are greatly improved. Furthermore, it is expected that the heat distortion temperature will rise and the hardness will improve.

As described above, it may be important to arrange the silicate plate, which is a cleavage product of the layered clay mineral contained in the resin, in a specific direction depending on the shape and purpose of the molded product. To evaluate the array state of the silicate plate, take the XRD of the composite resin, and calculate the spatial distribution of the diffraction intensity at 2θ corresponding to the diffraction intensity from the target silicate plate, for example, an XRD device equipped with a quadrupole goniometer. It is possible to know the arrangement state of the silicate plate in the resin composition by measuring with.

In order to solve the above-mentioned problems, the resin composite material according to a tenth aspect is characterized by being formed by mixing the flame-retardant resin composition with another resin.

In order to solve the above-mentioned problems, the resin composite material of claim 11 has an elastic modulus improved by 20% or more as compared with the other resin in which the flame-retardant resin composition is not blended. There is.

According to the above constitution, by mixing the flame-retardant resin composition with another resin, it is possible to improve the flame retardancy of the other resin and to improve the elastic modulus and the thermal decomposition temperature. Therefore, a flame-retardant and high-strength resin composite material can be obtained.

BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the present invention will be described below.

The flame-retardant resin composition of the present invention is highly flame-retardant by finely dispersing an organic salt-treated layered clay mineral in a resin containing a copolymer of ethylene and a polar monomer using a general-purpose mixer. It is a structure that has acquired the nature.

Further, the inventors of the present invention finely disperse the organic salt-treated layered clay mineral in a copolymer of ethylene and a polar monomer using a general-purpose mixer to obtain the flame retardancy inherent to the layered clay mineral. It was also confirmed that was further improved.

Examples of the layered clay mineral in the present invention include smectite clays such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, and mica. The layered clay minerals exemplified above may be natural or synthetic.

The organic salt treatment in the present invention means that the layered clay mineral is organized by ionically bonding an organic onium ion to the surface of the layered clay mineral. The layered clay mineral is preferably organically bonded by ionic bonding with an organic onium ion having 6 or more carbon atoms. When the number of carbon atoms is less than 6, the hydrophilicity of the organic onium ion may be increased and the compatibility with the polymer may be decreased.

Examples of the organic onium ion include hexyl ammonium ion, octyl ammonium ion, 2-ethylhexyl ammonium ion, dodecyl ammonium ion, lauryl ammonium ion, octadecyl ammonium ion, stearyl ammonium ion, dioctyl dimethyl ammonium ion, trioctyl ammonium ion. Ion, alkylamine such as distearyldimethylammonium ion, or ammonium laurate ion, or acrylamine,
Acetylamine, allylamine, alcoholamine, amine acetic acid, halogen-containing amine, aromatic-containing amine, sulfamine, thiamine, hydroxyl group-containing amine and the like can be used.

Examples of the copolymer of ethylene and polar monomer according to the present invention include ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, Examples thereof include ethylene-maleic acid copolymers and various ionomers of the above-exemplified copolymers.

The present inventors have found that when the above-mentioned copolymer of ethylene and polar monomer is modified, the organic salt-treated layered clay mineral is likely to be finely dispersed.

The modification means introducing a functional group into the copolymer in order to further accelerate the treatment with an organic salt. The modification of the copolymer can be performed with various modifiers such as acid anhydrides. The functional group to be introduced into the copolymer at the time of modification is not particularly limited, but one having high compatibility with an organic salt is desirable, and examples thereof include acid anhydride groups, carboxylic acid groups, hydroxyl groups, thiol groups, and epoxy groups. Group, halogen group, ester group, amide group, urea group, urethane group, ether group, thioether group, sulfonic acid group, phosphonic acid group, nitro group, amino group, oxazoline group, imide group,
Examples thereof include isocyanate group and maleic acid group.

As a method for treating the layered clay mineral of the present invention with an organic salt, for example, a solution in which an organic salt is dissolved is mixed with a layered clay mineral solution and a swelling solution, and a precipitate generated by this is mixed with an organic salt. Examples include a method of obtaining a salt-treated layered clay mineral.

As the solvent used for preparing the solution in which the organic salt is dissolved, the layered clay mineral solution, and the swelling solution, water, methanol, ethylformamide, nitromethane, ethanol, acrylic acid, acetonitrile, aniline, cyclo Hexanol, n-butanol, methylamine, n-amyl alcohol, acetone, methyl ethyl ketone, chloroform, benzene, ethyl acetate, toluene, diethyl ketone, carbon tetrachloride, benzonitrile, cyclohexane, isobutyl chloride, diethylamine,
Methylcyclohexane, isoamyl acetate, n-octane, n-heptane, isobutyl acetate, isopropyl acetate, methyl isopropyl ketone, butyl acetate, methyl propyl ketone, ethylbenzene, xylene, tetrahydrofuran, trichloroethylene, methyl ethyl ketone,
Examples thereof include methylene chloride, pyridine, n-hexanol, cyclohexanol, n-butanol, isopropyl alcohol, dimethylformamide, nitromethane, ethylene glycol, glycerolformamide, dimethyl sulfoxide and the like. The solvents exemplified above may be used alone or in combination of two or more.

The flame-retardant resin composition of the present invention is obtained by finely dispersing the organic salt-treated layered clay mineral in a resin containing a copolymer of ethylene and a polar monomer using, for example, a general-purpose mixer. Let me do it.

In the present invention, that the layered clay mineral is finely dispersed in the resin, that is, uniformly dispersed, means that a silicate plate, which is a cleavage product of the layered clay mineral, is preferably
Cleavage into individual sheets shows that this plate is dispersed in the resin without agglomeration.

Whether or not cleavage is performed one by one,
First, an X-ray diffraction diagram (hereinafter abbreviated as XRD) by X-ray diffraction of a resin composition containing a layered clay mineral before being treated with an organic salt.
And the XRD of the flame-retardant resin composition in which the layered clay mineral according to the present invention is treated with an organic salt and dispersed in a resin, and the layered structure in the XRD of the resin composition simply containing the layered clay mineral before the organic salt treatment The diffraction intensity (I (0)) at the diffraction angle (2θ (0)) corresponding to the clay mineral and the diffraction intensity (I) from the flame-retardant resin composition which is a fine dispersion of the layered clay mineral treated with the organic salt.
(1)) and compare. At this time, in the present invention, I (1) / I
(0) is 0.75 or less, preferably 0.5 or less, and particularly preferably 0.25 or less. If this value is greater than 0.75, there are many uncleavable products, and the degree to which the moldability, the physical properties of the obtained molded product, and the performance are improved is low.

Further, depending on the decrease in the diffraction intensity at 2θ, new diffraction may occur at a lower angle. This is a resin of a layered clay mineral whose interlayer distance is increased by the organic salt treatment. This intensity is due to the dispersion in I '(1)
Is preferably at most twice the I (0), more preferably at most 1.5 times. It is also preferable that the value of 2θ that maximizes the diffraction intensity is shifted to the low angle side, and is usually adjusted so as to be shifted by at least 0.5 °, preferably at least 1.0 °.

As a method for finely dispersing, for example, a general method conventionally used can be used in addition to the method using the above-mentioned general-purpose mixer.

As a general-purpose mixer used for finely dispersing the organic salt-treated layered clay mineral of the present invention in a resin containing a copolymer of ethylene and a polar monomer, for example, roll, kneader, Banbury mixer, A kneading machine such as an intermix, a single-screw extruder or a twin-screw extruder can be used.

The flame-retardant resin composition of the present invention is a sheet-shaped or film-shaped material in which at least ½ of the organic salt-treated layered clay mineral is arranged in parallel to the sheet surface or the film surface. It may be. Further, in the flame-retardant resin composition of the present invention, at least 1/2 of the organic salt-treated layered clay mineral is arranged parallel to the circumferential surface (side surface of the cylinder) of the fiber or rod (cylindrical). Fibrous material or rod-shaped material
It may be a (cylindrical substance).

When the molded product is a two-dimensional molded product such as a film or a sheet, a layered clay mineral (eg, silicate plate) cleaved from the organic salt-treated layered clay mineral is arranged parallel to the film surface or the sheet surface. Things are preferred. For example, in order to improve the flame retardancy as in the present invention,
In order to reduce the amount of oxygen passing through the film, it is preferable that the surface of the layered clay mineral be arranged parallel to the film surface. For example, the ratio of the layered clay mineral arranged parallel to the film surface to the total layered clay mineral is usually at least 1/2, and more preferably at least 2/3.

In the present invention, when the layered clay mineral is one having a large aspect ratio such as the above fibrous material or rod-shaped material, the layered clay mineral arranged parallel to the circumferential direction or the side surface of the cylinder (for example, The ratio of the silicate plate) to the whole layered clay mineral is usually at least 1/2, more preferably at least 2/3.

In order to arrange the layered clay minerals in a specific direction, there are, for example, a method of applying a constant stress, a method of applying a constant deformation, and a method of applying an electric field or a magnetic field. A suitable method can be selected according to need.

The resin according to the present invention refers to a high molecular compound such as rubber or plastic, and includes the above-exemplified copolymer of ethylene and a polar monomer and, if necessary, other high molecular compounds. May be.

That is, the resin according to the present invention contains a polymer compound other than the above-mentioned copolymer, in addition to the above-mentioned copolymer of ethylene and a polar monomer, if necessary using a compatibilizer. May be. As the polymer compound other than the copolymer contained in the resin, specifically, for example, ABS resin (acrylonitrile-butadiene-styrene copolymer), ACS resin, alkyd resin, amino resin, ASA resin, Bismaleimide triazine resin, errol plastic resin, chlorinated polyether, chlorinated polyethylene, allyl resin, epoxy resin, ethylene
α-olefin copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, EV
A (ethyl vinyl alcohol) resin, FRP (fiber re
inforced plastic), ionomer, methacryl-styrene copolymer, nitrile resin, polyester, olefin-vinyl alcohol copolymer, petroleum resin, phenol resin, polyacetal, polyacrylate, polyallylsulfone, polybenzimidazole, polybutadiene, polybutylene, poly Butylene terephthalate, polycarbonate, polyether ether ketone, polyether ketone, polyether nitrile, polyether sulfone, polyethylene, polyethylene terephthalate,
Polyketone, methacrylic resin, polymethylpentene, polypropylene, polyphenylene ether, polyphenylene sulfide, polysulfone, polystyrene, SAN
Resin, butadiene-styrene resin, polyurethane, polyvinyl acetal, polyvinyl alcohol, polyvinyl chloride (PVC resin), polyvinylidene chloride, silicone resin, polyvinyl acetate, xylene resin, nylon, fluororesin, liquid crystal polymer, thermoplastic elastomer, ethylene Propylene rubber (EPDM), Chloroprene rubber (CR),
Butadiene rubber (BR), nitrile rubber, natural rubber, acrylonitrile butadiene rubber, butyl rubber, fluororubber, styrene butadiene rubber, polysulfide rubber, urethane rubber, silicone rubber, chlorinated polyethylene, epichlorohydrin rubber, chlorosulfonated polyethylene, etc. Examples include rubber and plastics. These are used alone or in combination of two or more.

In the resin composition of the present invention, the layered clay mineral treated with the organic salt of the present invention is added to 100 parts by weight of the copolymer of ethylene and a polar monomer in the resin composition.
The content is more preferably 0.1 to 100 parts by weight, further preferably 0.1 to 50 parts by weight, and most preferably 1 to 30 parts by weight.

Since the layered clay mineral treated with the organic salt is contained in the resin containing the copolymer of ethylene and the polar monomer and the modified resin composition thereof in the above-mentioned predetermined ratio, the resin composition is burned. Flame retardancy can be improved at times. More specifically, according to the above configuration, J
25 in the limiting oxygen index test specified by IS K 7201
It is possible to obtain flame retardancy above the point.

Alternatively, the maximum calorific value of the flame-retardant resin composition containing the organic salt-treated layered clay mineral defined in ASTM E 1354 is compared with the maximum calorific value of the resin alone defined in ASTM E 1354. It has been confirmed that the flame retardancy is also improved by improving the heat resistance of the resin itself, and the mechanical properties are also significantly improved in the present invention. Therefore, by adding the flame-retardant resin composition according to the present invention to another resin as a masterbatch, the other resin can be improved.

Other resins to be mixed with the flame-retardant resin composition of the present invention include, for example, ABS resin (acrylonitrile-butadiene-styrene copolymer), ACS resin, alkyd resin, amino resin, ASA resin, bis resin. Maleimide triazine resin, errol plastic resin, chlorinated polyether, chlorinated polyethylene, allyl resin, epoxy resin, ethylene-α-olefin copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer Combined, EVA (ethyl vinyl alcohol) resin, FRP (fiber reinforced plastic), ionomer, methacryl-styrene copolymer, nitrile resin, polyester, olefin-vinyl alcohol copolymer,
Petroleum resin, phenol resin, polyacetal, polyacrylate, polyallyl sulfone, polybenzimidazole, polybutadiene, polybutylene, polybutylene terephthalate, polycarbonate, polyether ether ketone, polyether ketone, polyether nitrile, polyether sulfone, polyethylene, polyethylene terephthalate , Polyketone, methacrylic resin, polymethylpentene, polypropylene, polyphenylene ether, polyphenylene sulfide, polysulfone,
Polystyrene, SAN resin, butadiene-styrene resin, polyurethane, polyvinyl acetal, polyvinyl alcohol, polyvinyl chloride (PVC resin), polyvinylidene chloride, silicone resin, polyvinyl acetate, xylene resin, nylon, fluorine resin, liquid crystal polymer, thermoplastic Elastomer, ethylene propylene rubber, chloroprene rubber, butadiene rubber, nitrile rubber, natural rubber, acrylonitrile butadiene rubber, butyl rubber, fluorine rubber, styrene butadiene rubber, polysulfide rubber, urethane rubber, silicone rubber, chlorinated polyethylene, epichlorohydrin rubber, Examples include rubber and plastics such as chlorosulphonated polyethylene. These are used alone or in combination of two or more. It is considered that the resin to be mixed with the flame-retardant composition has improved dispersibility even when the compatibilizer is mixed and used.

Examples thereof include polymers having a double bond, a carboxy group, an epoxy group and the like, random copolymers, graft block copolymers, oxazoline compounds and the like.

The flame-retardant resin composition of the present invention and the resin composite material using the same are used for all materials requiring flame-retardant properties, such as electric wires, hoses, films, coating materials, sheets, footwear and packing. It can be particularly preferably used for industrial pipes such as gas pipes and electric wires, and plastic materials for housing such as rain gutters.

In addition to the above-exemplified materials, the flame-retardant resin composition of the present invention can be used, for example, as electric wires / cables, artificial grass mats, tires, saddles, lids of sealed containers, container stoppers, ski equipment, Mudguard, baby products, foot rubber, bottom material,
Golf equipment, tuners, toys, bellows tubes, floats, ice machines, foot pumps, droppers, bidets, bath shoes, rubber balls, agricultural films, liquid containers, medium weight packaging films, adhesion / protection films, adhesives, field products Sheets, low-temperature seal packaging materials, washing machine drainage hoses, protective pipes, spiral sleeves, construction civil waterproofing sheets, sash gaskets, packing, upholstery products, home appliance housings, vehicle parts, aircraft parts, gas parts, garbage bags , Food packaging wraps, and the like. Further, also in applications other than the above, the flame-retardant resin composition of the present invention can be used as a heating source for electricity, gas, oil, coal, nuclear power, plasma generators, etc., plastic parts of machines and devices, plastic parts of buildings. , And plastic parts of vehicles. For example, air conditioners, radios, televisions, fans, dishwashers, microwave ovens, juicers and mixers, cookers, washing machines, audio equipment, video appliances, snap switches, cord wires, plug receptacles, and printed circuit boards. ,
Cordsets / power cords, temperature display control boards, electronic components such as transformers, electric wires, connector products, curtains, wallpaper, walls, beams, floors, building materials such as carpets, vehicle materials such as seats, panels, floors and insulation materials And so on.

When used for the above-exemplified uses, the flame-retardant resin composition of the present invention may optionally contain an additive which is usually added. Examples of the additives include cross-linking agents, cross-linking accelerators, cross-linking promoting aids, activators, cross-linking inhibitors, anti-aging agents, antioxidants, anti-ozonants, UV absorbers, light stabilizers, tackifiers. , Plasticizers, softeners, reinforcing agents, reinforcing agents, foaming agents, foaming aids, stabilizers, lubricants, release agents, antistatic agents, modifiers, colorants, coupling agents, preservatives, antifungal agents, Modifiers, adhesives, perfumes, polymerization catalysts, polymerization initiators, polymerization inhibitors, polymerization inhibitors, polymerization regulators, polymerization initiators, crystal nucleating agents, compatibilizers, dispersants, defoamers, etc. Can be mentioned. These can be used alone or in combination of two or more.

[0063]

EXAMPLES Next, specific examples of the present invention will be described by showing experimental results. However, the present invention is not limited to the following examples.

<Flame Retardancy Test Method> The flame retardance test method is oxygen index measurement JIS K7201 and / or ASTM E 1354.
A corn calorimeter test was performed.

<Mechanical properties> Mechanical properties are JIS K7
Quantified by 113.

[Example 1] Layered clay mineral (Kunipia F
Water produced by heating 10 g of Kunimine Industries Co., Ltd. to 80 ° C 1000 m
A mixed solution prepared by mixing in 1 was prepared. Next, the mixed solution,
Prepare a preparation solution consisting of 10 g of dodecylamine and 3 ml of concentrated hydrochloric acid, stir at 80 ° C for 12 hours, filter, and further 80 ° C.
The filter cake was washed with 3000 ml of water. The obtained filter cake was freeze-dried to obtain a layered clay mineral treated with an organic salt.

Next, 10 parts by weight of the organic salt-treated layered clay mineral obtained above was mixed with 100 parts by weight of ethylene vinyl acetate (EV260 manufactured by Mitsui DuPont Co., Ltd.) to prepare a twin-screw centrifugal extruder (Technobel Co., Ltd.). , KZW15-30M
G) was kneaded to prepare a flame-retardant resin composition, which was molded into a sheet. The set temperature of the twin-screw centrifugal extruder was 120 ° C. for the feed section, 120 ° C. for the kneading section, and 120 ° C. for the discharge section, and the screw rotation speed was 60 rpm. By the above method, the flame retardancy of the flame-retardant resin composition (limit oxygen index, maximum calorific value of cone calorimeter (unit: kw / m ² )), mechanical properties (elastic modulus (unit: Mpa), maximum stress ( Unit: Mp
a) and elongation (%)) were examined. The results are shown in Table 1.

Example 2 100 parts by weight of ethylene vinyl acetate (EV260 manufactured by Mitsui DuPont), 10 parts by weight of an organic salt-treated layered clay mineral, 0.1 g of dicumyl peroxide (Kayaku Akzo DCP40),
A flame-retardant resin composition was obtained in the same manner as in Example 1 except that 1 g of maleic anhydride was mixed. The flame retardancy and mechanical properties of the flame retardant resin composition were examined by the above method.
The results are shown in Table 1. [Comparative Example 1] A resin composition for comparison was obtained in the same manner as in Example 1, except that only ethylene vinyl acetate (EV260 manufactured by Mitsui DuPont) was molded into a sheet. By the above method, the flame retardancy and mechanical properties of the resin composition for comparison were examined. The results are shown in Table 1.

[Comparative Example 2] 10 parts by weight of a layered clay mineral (Kunipia F, Kunimine Industry Co., Ltd.) was added to 100 parts by weight of ethylene vinyl acetate (EV260, manufactured by Mitsui DuPont).
By mixing the parts by weight, a twin-screw centrifugal extruder (Technobel, KZ
W15-30MG) was kneaded to prepare a comparative resin composition, which was molded into a sheet. The set temperature of the twin-screw centrifugal extruder was 120 ° C. for the feed section, 120 ° C. for the kneading section, and 120 ° C. for the discharge section, and the screw rotation speed was 60 rpm.
With respect to the obtained comparative resin composition, the flame retardancy and mechanical properties of the flame retardant resin composition were examined by the above-mentioned methods.
The results are shown in Table 1.

[0070]

[Table 1] From the results in Table 1, it can be seen that the flame-retardant resin composition of the present invention has good flame retardancy and mechanical properties as compared with the comparative resin composition.

Examples 1 and 2 shown in FIGS.
FIG. 2 shows the X-ray diffraction data of Comparative Example 2. Also, FIG.
The X-ray diffraction data of Examples 1 and 2 and Comparative Examples 1 and 2 are shown in FIG. In Comparative Example 2 shown in FIG. 2, there is a Kunipia F peak near 7 degrees of 2θ, but in Example 1, the peak is 2θ = 5.5 °, as shown in FIG. 2.75 °
It can be seen that the layers of the layered clay mineral are considerably open due to the organic salt treatment. In the second embodiment, as shown in FIG.
As shown in (b), it can be seen that the angle is shifted to the low angle side of 2θ = 5.8 ° and that the peak is almost disappeared. From this, it can be seen that Example 2 is not completely in the initial state of the layered clay mineral but is finely dispersed in the silicate plate forming the same. Further, in Comparative Example 1, a diffraction peak of montmorillonite appears only at 2θ = 7.1 °, indicating that the clay mineral exists in a state where it is hardly cleaved. Further, the flame-retardant resin composition of Example 1 was pressed by a hot press to form a sheet having a thickness of about 0.1 mm, and the XRD was taken in the direction parallel to the film surface and the direction perpendicular thereto. The diffraction angles are both 2θ = 5.42 °,
The diffraction intensity is about 2/3 of the diffraction intensity in the direction perpendicular to the sheet surface compared to the direction parallel to the sheet surface, and the cleaved silicate plates are preferentially arranged in parallel to the sheet surface. showed that. It can be seen that this structural feature also results in a high limit oxygen index value (excellent flame retardancy) in Example 1.

Further, as is apparent from FIG. 3, the diffraction intensity I at the diffraction angle (2θ (0), which is 7.1 ° for montmorillonite, for example), which is the starting point, peculiar to each type of layered clay mineral.
When (0) was compared with the diffraction intensity I (1) of the organic salt-treated layered clay mineral finely dispersed in the resin, in Example 1, I (1) / I (0) was 0.5. And in Example 2,
It is around 0, and both I (1) / I (0) are 0.75 or less.

Next, FIG. 4 shows the relationship between the heat release rate (HRR; Heat Release Rate) in the cone calorimeter (CCR) and the burning time. As shown in the figure, the maximum HRR of Comparative Example 1 is about 2
It is as high as 999kw / m ² , but in Comparative Example 2 it is about half of that.
It becomes 1699kw / m ² . The maximum HRR of Example 2 is about 1 / of that of Comparative Example 1.
3 was 1117 kw / m ² , and the maximum HRR of Example 1 was about 1/4 of Comparative Example 1, which was 785 kw / m ² . Therefore, it is understood that the flame retardant effect is exhibited in Example 1 and Example 2 in which montmorillonite is finely dispersed in EVA.

[0074]

The flame-retardant resin composition of the present invention has a structure in which an organic salt-treated layered clay mineral is finely dispersed in a resin containing a copolymer of ethylene and a polar monomer.

Therefore, the organic salt-treated layered clay mineral is uniformly dispersed in a copolymer of ethylene and a polar monomer, for example, by kneading with a general-purpose mixer, which results in high flame retardancy. Obtainable. Thereby, a flame-retardant resin composition having high flame retardancy can be provided. Further, since the organic salt-treated layered clay mineral can be uniformly dispersed in the copolymer of polar monomers by a general-purpose mixer, the mechanical properties are also good. Furthermore, by using a general-purpose mixer without using a special kneading method or a kneading device, it is possible to obtain excellent mechanical properties, which leads to cost reduction in production and a cheaper flame-retardant resin composition. There is an effect that it can be provided.

By mixing the flame-retardant resin composition of the present invention with another resin as a reinforcing agent, etc., it is possible to provide a resin composite material having not only flame retardancy but also high strength. .

[Brief description of drawings]

FIG. 1A is a graph showing X-ray diffraction data of a flame-retardant resin composition according to an embodiment of the present invention.
(B) is a graph showing X-ray diffraction data of a flame-retardant resin composition according to another embodiment of the present invention.

FIG. 2 is a graph showing X-ray diffraction data of a resin composition for comparison.

FIG. 3 is a graph showing X-ray diffraction data of the flame-retardant resin compositions of Examples 1 and 2 and a comparative resin composition.

FIG. 4 is a graph showing the relationship between the heat generation rate and the burning time of a cone calorimeter of the flame-retardant resin compositions of Examples 1 and 2 and a comparative resin composition.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hajime Kambara             19-204, 26-26, Fujimidai, Nerima-ku, Tokyo             issue F term (reference) 4J002 BB041 BB061 DJ036 FB086                       FD016 FD136

Claims (11)

[Claims] 1. A flame-retardant resin composition characterized in that an organic salt-treated layered clay mineral is finely dispersed in a resin containing a copolymer of ethylene and a polar monomer. 2. A diffraction intensity (I (0)) at a diffraction angle (2θ (0)) corresponding to a layered clay mineral not treated with an organic salt, and an organic substance finely dispersed in the resin, which are obtained by X-ray diffraction. Compared with the diffraction intensity (I (1)) of the layered clay mineral treated with salt, I (1)
The flame-retardant resin composition according to claim 1, wherein the organic salt-treated layered clay mineral is finely dispersed in the resin within a range in which / I (0) is 0.75 or less. 3. A layered clay mineral treated with an organic salt, relative to 100 parts by weight of a copolymer of ethylene and a polar monomer,
The flame-retardant resin composition according to claim 1, which is contained in an amount of 0.1 to 100 parts by weight. 4. The flame-retardant resin composition according to any one of claims 1 to 3, which has an oxygen index defined by JIS K 7201 of 25 or more. 5. The maximum calorific value of the flame-retardant resin composition containing the organic salt-treated layered clay mineral defined in ASTM E 1354 is compared with the maximum calorific value of the resin alone specified in ASTM E 1354. It is less than or equal to three-quarters.
The flame-retardant resin composition according to any one of 1 to 3. 6. The flame retardant resin composition according to any one of claims 1 to 5, wherein the copolymer is an ethylene-vinyl acetate copolymer. 7. The flame-retardant resin composition according to claim 1, wherein the copolymer is modified. 8. The sheet-like material or film-like material in which at least 1/2 of the organic salt-treated layered clay mineral is arranged in parallel with the sheet surface or the film surface. The flame-retardant resin composition according to any one of items. 9. An organic salt-treated layered clay mineral in which at least 1/2 is a fibrous substance or rod-shaped substance arranged in parallel to the fiber or rod side face.
The flame-retardant resin composition according to any one of 1. 10. A resin composite material, which is obtained by mixing the flame-retardant resin composition according to any one of claims 1 to 9 with another resin. 11. The resin composite material according to claim 10, wherein an elastic modulus is improved by 20% or more as compared with the other resin in which the flame retardant resin composition is not blended.