JP2003171569A - Fire retarding resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fire retarding resin composition in which a fire retarding property is excellent, a fire retarding effect is particularly exhibited by a shape retaining effect at the time of burning and mechanical strengths and thermal characteristics are excellent. <P>SOLUTION: The fire retardant resin composition contains 100 parts by weight of a thermoplastic resin, 0.1-20 parts by weight of laminar silicate and 1-150 parts by weight of a non-halogen type fire retarding agent. In the laminar silicate, single layers of at least a part of the laminar crystal are superposed so as to deviate centers of surfaces of the single layer. The laminar silicate becomes a flat plate-like shape having a thickness of 5-50 nm and a length of 500 nm or more on appearance and is dispersed. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition which is excellent in flame retardancy, particularly exhibits a flame-retardant effect due to a shape-retaining effect during combustion, and further has excellent mechanical strength and thermal properties.

[0002]

2. Description of the Related Art In recent years, polyolefin resins such as polyethylene resins and polypropylene resins have attracted attention as environmentally friendly materials as substitutes for polyvinyl chloride due to the problems of waste plastic treatment and environmental hormones.

However, since the polyolefin resin is non-polar, it is very difficult to exhibit functions such as printability, adhesiveness and flame retardancy. In particular, polyolefin resin is one of the resins with the highest flammability, and achieving flame retardancy is the most difficult issue. At present, there are many cases in which a flame retardant is kneaded into a polyolefin resin for use.

Among the flame retardants, the halogen-containing flame retardant has a high flame retarding effect, and the deterioration of the moldability and the mechanical strength of the molded product are relatively small. There is a possibility that a large amount of halogen-based gas may be generated during combustion, and the generated gas may corrode the equipment or affect the human body, so from the viewpoint of safety, so-called non-halogen flame retardant A chemical treatment method has been strongly desired.

As one of the non-halogen flame retardant technologies for polyolefin resins, no toxic gas is generated during combustion,
A method of adding a metal compound such as aluminum hydroxide, magnesium hydroxide or basic magnesium carbonate to a polyolefin resin is disclosed in JP-A-57-165437 and JP-A-61-36343.

However, in order to impart sufficient flame retardancy to the flammable polyolefin resin, it is necessary to add a large amount of a metal compound, and as a result, the mechanical strength of the obtained molded product is significantly lowered. However, there was a problem that it was difficult to put it into practical use. Among them, aluminum hydroxide,
When a metal hydroxide such as magnesium hydroxide is added to a polyolefin resin, a coating layer cannot be formed during combustion, brittle ash is exposed, and residues fall off. In addition to its early loss of function, it was not possible to stop the spread of fire due to the deformation of the material.

Further, a method has been proposed in which a phosphorus-based flame retardant is added to a polyolefin-based resin to utilize the oxygen barrier effect by forming a surface film during combustion to develop flame retardancy. However, in order to impart sufficient flame retardancy to the flammable polyolefin resin, it is necessary to add a large amount of phosphorus-based flame retardant, and as a result, the mechanical strength of the resulting molded article is significantly reduced. However, there was a problem that it was difficult to put it into practical use. When a phosphorus-based flame retardant is added to a polyolefin-based resin, a film is locally formed,
A strong coating layer cannot be formed as a continuous layer.
Also, the local mechanical strength of the coating is very weak, and during combustion, brittle ash is exposed and the residue falls off,
In addition to losing the function as a heat insulating layer at an early stage, it was not possible to stop the spread of fire due to the deformation of the material.

Japanese Unexamined Patent Publication No. 6-2476 discloses a resin composition obtained by adding red phosphorus or a phosphorus compound and expandable graphite to a polyolefin resin. This resin composition has sufficient flame retardancy when viewed from the oxygen index, but can form a film only locally and cannot form a strong film layer as a continuous layer. Also, the local mechanical strength of the coating is very weak, and during combustion, brittle ash is exposed and the residue falls off,
In addition to losing the function as a heat insulating layer at an early stage, it was not possible to stop the spread of fire due to the deformation of the material.

Therefore, when a polyolefin resin is used as a flame-retardant material, for example, in the form of a sheet and used as a wall lining material, the temperature of the back surface is reduced to 260 ° C. or lower when the surface is heated to 1000 ° C. JIS A 1 to suppress
It does not meet the criteria for fire resistance test and fire protection test based on 304, and not only does it have insufficient fire resistance, but after burning, only brittle ash remains and the residue falls off, so the function as a heat insulation layer is early. There was a problem of losing to.

[0010]

SUMMARY OF THE INVENTION In view of the above situation, the present invention has excellent flame retardancy, in particular exhibits a flame retardant effect by the shape retaining effect during combustion, and further has excellent mechanical strength and thermal characteristics. An object is to provide a fuel resin composition.

[0011]

The present invention provides a flame retardant resin composition containing 100 parts by weight of a thermoplastic resin, 0.1 to 100 parts by weight of a layered silicate, and 1 to 150 parts by weight of a halogen-free flame retardant. In the layered silicate, at least a part of the monolayers of the layered crystals are overlapped with each other by shifting the centers of the monolayer surfaces, and apparently the thickness is 5 to 50 nm and the length is 50 nm.
It is a flame-retardant resin composition that is dispersed in the form of a flat plate of 0 nm or more. The present invention is described in detail below.

The flame-retardant resin composition of the present invention contains a thermoplastic resin, a layered silicate, and a halogen-free flame retardant. The thermoplastic resin is not particularly limited, and examples thereof include polyolefin resin, polystyrene resin, acrylonitrile-butadiene-styrene resin, polyethylene terephthalate resin, poly (meth) acrylic acid ester resin, silicone resin, polyamide resin, polyurethane resin, polycarbonate. Examples thereof include resins, polyimide resins, polyphenylene sulfide resins, polyether sulfone resins and the like. Among them, polyolefin resin is preferably used.

The above polyolefin resin is obtained by polymerizing an olefin monomer having a polymerizable double bond in the molecule. The olefin-based monomer is not particularly limited, and examples thereof include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-
Examples include α-olefins such as octene and 4-methyl-1-pentene; dienes such as butadiene; cyclic olefins such as norbornene-based monomers. The substituent in the substitution product of the norbornene-based monomer is not particularly limited as long as it is a conventionally known one, which is either a hydrocarbon group or a polar group, and examples thereof include an alkyl group, an alkylidene group, an aryl group, and a cyano group. Groups, halogen atoms, alkoxycarbonyl groups, pyridyl groups and the like. Specific examples of the norbornene-based monomer include, for example, norbornene, methanooctahydronaphthalene, dimethanooctahydronaphthalene, dimethanodecahydroanthracene,
Dimethanodecahydroanthracene, trimetanododecahydroanthracene, dicyclopentadiene, 2,3-dihydrocyclopentadiene, methanooctahydrobenzoindene, dimethanooctahydrobenzoindene, methanodecahydrobenzoindene, dimethanodecahydrobenzoindene, Methanooctahydrofluorene, dimethanooctahydrofluorene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene,
5-ethylidene-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5-phenyl- 5-methyl-2-norbornene and the like can be mentioned.
These norbornene-based monomers may be used alone or in combination of two or more.

Examples of the polyolefin resin include homopolymers of propylene, copolymers of propylene and α-olefins, random or block copolymers of propylene and ethylene, homopolymers of ethylene, ethylene and α. -Copolymer with olefin, ethylene and (meth)
Acrylic acid copolymer, ethylene and (meth) acrylic acid ester copolymer, ethylene and vinyl acetate copolymer, butene homopolymer, isoprene homopolymer, butadiene and other diene Homopolymers and copolymers, alicyclic hydrocarbon resins and the like can be mentioned. Among them, homopolymers of propylene, α other than propylene and C3
A copolymer with an olefin, a homopolymer of ethylene, a copolymer of ethylene with an α-olefin having 3 or more carbon atoms, an acrylic acid ester, a vinyl acetate and the like are preferably used. As the polymer of the norbornene-based resin that can be obtained as a commercially available product, for example, Arton (manufactured by JSR), Zeonoa (manufactured by Nippon Zeon Co., Ltd.) and the like are preferably used. These may be used alone or in combination of two or more.

The molecular weight and molecular weight distribution of the thermoplastic resin are not particularly limited, but the preferred lower limit of the weight average molecular weight is 5000 and the upper limit thereof is 5,000,000. A more preferable lower limit is 20,000 and an upper limit is 300,000. Also, the weight average molecular weight /
The preferable lower limit of the molecular weight distribution represented by the number average molecular weight is 1.1 and the upper limit is 80. A more preferable lower limit is 1.
5, the upper limit is 40.

Additives may be appropriately added to the thermoplastic resin in order to obtain desired physical properties. The additive is not particularly limited, and examples thereof include an antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, and an antistatic agent. Also, a small amount of a substance that can serve as a crystal nucleating agent may be added to the above-mentioned thermoplastic resin to assist in homogenizing the physical properties, thereby making the crystals finer.

The flame-retardant resin composition of the present invention contains a layered silicate. In the present specification, the layered silicate means a silicate mineral having an exchangeable cation between layers of layered crystals.

The layered silicate is not particularly limited,
Examples thereof include smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, and swelling mica. Among these, smectites and swelling mica having a large shape anisotropy effect defined by the following formula (1) are preferable from the viewpoint of mechanical strength of the composite material. Shape anisotropy effect = area of surface of layered crystal / area of side surface of layered crystal (1) The layered silicate may be a natural product or a synthetic product. These layered silicates may be used alone or in combination of two or more. The surface of the layered crystal and the side surface of the layered crystal in the above formula (1) are shown in FIG.

The exchangeable cations existing between the layers of the layered crystal of the layered silicate are ions such as sodium and calcium on the surface of the layered crystal, and these ions have an ion exchange property with the cationic substance. Therefore, various cationic substances can be inserted between the layers of the layered crystal of the layered silicate.

The cation exchange capacity of the layered silicate is not particularly limited, but the preferred lower limit is 50 milliequivalent /
100 g, the upper limit is 200 milliequivalents / 100 g. 5
If it is less than 0 milliequivalent / 100 g, the amount of the cationic substance intercalated between the layers of the layered crystal by ion exchange may be small, and the layers may not be sufficiently depolarized. If it exceeds 100 g, the bonding force between the layers of the layered crystal becomes strong, and the crystal flakes may be difficult to peel off.

In the layered silicate, the interlayers of the layered crystal are cation-exchanged with a cationic surfactant in advance to make them hydrophobic, thereby enhancing the affinity between the layered silicate and the thermoplastic resin, and Can be finely dispersed uniformly.

The cationic surfactant is not particularly limited, and examples thereof include a quaternary ammonium salt and a quaternary phosphonium salt. Among them, a quaternary ammonium salt having an alkyl chain having 6 or more carbon atoms, that is, an alkylammonium salt is preferably used because it can sufficiently depolarize the layers of the layered crystal of the layered silicate. Examples of the quaternary ammonium salt include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl ammonium salt, distearyl dimethyl ammonium salt, di-hardened tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, dipolyoxyethylene alkyl. Examples thereof include methyl ammonium salt and polyoxypropylene methyl diethyl ammonium salt. Examples of the quaternary phosphonium salt include dodecyltriphenylphosphonium salt (DTPB), methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, trioctylphosphonium salt, distearyldimethylphosphonium salt, distearyldibenzyl. Examples thereof include phosphonium salts.

The lower limit of the amount of the layered silicate compounded is 0.1 parts by weight and the upper limit is 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
Parts by weight. If it is less than 0.1 parts by weight, it becomes difficult to form a sintered body, so that the flame retarding effect is small, and if it exceeds 20 parts by weight, the density of the flame retardant resin composition becomes high and the practicality is lost. . The preferred lower limit is 0.5 parts by weight and the upper limit is 15.
Parts by weight.

In the flame-retardant resin composition of the present invention, as shown in FIG. 2, in the layered silicate, at least a part of the monolayers of the layered crystals are apparently overlapped with each other by shifting the centers of the monolayer surfaces. In addition, it is dispersed in the form of a flat plate (hereinafter also referred to as a playing card) having a thickness of 5 to 50 nm and a length of 500 nm or more. As the layered silicate disperses in a trump shape and is dispersed, as compared with the case where the single layer of the layered silicate layered crystals are dispersed as shown in FIG. Is suppressed, and the layered silicate easily sinters during combustion, improving the effect of suppressing combustion. In order to exert the effect with a smaller addition amount, the preferable upper limit of the apparent thickness of the layered silicate is 30 nm and the preferable upper limit of the length thereof is 5 μm. The more preferable upper limit of the thickness is 15 nm and the more preferable upper limit of the length is 2 μm.

The method of dispersing the layered silicate in the resin in the form of a card is not particularly limited, and examples thereof include a method of melt-kneading the resin and the organically modified layered silicate, and a method of further adding a dispersant. Can be mentioned. By using these dispersion methods, the layered silicate can be more uniformly and finely dispersed. When the resin is a resin having low polarity such as polypropylene, the method using a dispersant is preferable because it is easy to handle and the orientation of the layered silicate is easy to control. The dispersant preferably has a polar group, for example, a copolymer of ethylene and (meth) acrylic acid, a copolymer of ethylene and (meth) acrylic acid ester, a copolymer of ethylene and vinyl acetate. Examples include coalescence. The preferable lower limit of the compounding amount of the dispersant is 1% by weight, and the upper limit thereof is 20% by weight, based on the whole resin. When it is 1% by weight or less, the dispersion and orientation of the layered silicate may be insufficient, and when it exceeds 20% by weight, the physical properties may be deteriorated.

The method for melt-kneading the resin and the layered silicate is not particularly limited, and examples thereof include a method of melt-kneading with an extruder, a two-roll, a Banbury mixer, etc., where both the resin and the layered silicate are dissolved. And a method of mixing in an organic solvent.

The flame-retardant resin composition of the present invention contains a non-halogen flame retardant. The non-halogen flame retardant is not particularly limited, but, for example, phosphorus compounds, metal hydroxides, melamine derivatives and the like are preferably used. The non-halogen flame retardants may be used alone or in combination of two or more.

The phosphorus compound is not particularly limited, and examples thereof include red phosphorus, ammonium polyphosphate, and phosphorus compounds represented by the following formula (1). These phosphorus compounds may be used alone or in combination of two or more.

[0029]

[Chemical 1]

In the above formula (1), R ¹ and R ³ represent a hydrogen atom, an alkyl group having 1 to 16 carbon atoms or an aryl group, and R ² represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 16 carbon atoms. Represents a group, an alkoxyl group, an aryl group or an aryloxy group. If the alkyl group has more than 16 carbon atoms, the relative content of phosphorus decreases, and the flame retardancy-imparting effect may be insufficient. In addition, R ¹ , R ² and R ³ may be the same or different.

The phosphorus compound represented by the above formula (1) is not particularly limited, and examples thereof include methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid and 2-methyl-. Propylphosphonic acid, t-butylphosphonic acid, 2,3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, Dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, bis (4-methoxyphenyl) phosphinic acid and the like can be mentioned. These phosphorus compounds may be used alone or in combination of two or more.

The red phosphorus is not particularly limited,
For example, in order to improve the moisture resistance and to prevent spontaneous ignition at the time of adding to the resin and kneading, it is preferable that the surface is coated with the resin. The ammonium polyphosphate is not particularly limited and may be, for example, one that has been subjected to a surface treatment such as melamine modification.

The metal hydroxide is not particularly limited, and examples thereof include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, dawsonite, calcium aluminate, gypsum dihydrate, and the like. Magnesium and aluminum hydroxide are preferably used. These metal hydroxides may be used alone or in combination of two or more. When two or more kinds of metal hydroxides are used in combination, the respective metal hydroxides start the decomposition dehydration reaction at different temperatures, so that a higher flame retardancy imparting effect can be obtained.

The metal hydroxide may be surface-treated with a surface-treating agent. The surface treatment agent is not particularly limited, and examples thereof include a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a polyvinyl alcohol surface treatment agent, an epoxy surface treatment agent, and a higher fatty acid surface treatment agent. Etc. These surface treatment agents may be used alone or in combination of two or more kinds.

Since the metal hydroxide undergoes an endothermic dehydration reaction under high heat during combustion, it absorbs heat and releases water molecules, thereby lowering the temperature of the combustion section and extinguishing the fire. Moreover, since the flame-retardant resin composition of the present invention contains a layered silicate, the effect of improving flame retardancy by the metal hydroxide is further increased. This is because the flame retardancy improving effect based on the film formation of the layered silicate during combustion and the flame retardance improving effect based on the endothermic dehydration reaction of the metal hydroxide occur competitively,
This is because each effect is promoted.

The melamine derivative is not particularly limited, and examples thereof include melamine, melamine cyanurate, melamine isocyanurate, melamine phosphate, and those obtained by subjecting these to a surface treatment. These melamine derivatives may be used alone or in combination of two or more. The surface treatment is not particularly limited, and examples thereof include the same surface treatment as that performed on the metal hydroxide.

The preferred lower limit of the amount of the non-halogen flame retardant compounded is 1 part by weight based on 100 parts by weight of the thermoplastic resin.
The upper limit is 150 parts by weight. If it is less than 1 part by weight, a sufficient flame retardancy improving effect may not be obtained. When it exceeds 150 parts by weight, the flame-retardant resin composition of the present invention has improved flame retardancy, but lowers mechanical strength and increases specific gravity.
This may cause defects in physical properties such as lack of flexibility, or may hinder the formation of a layered silicate sintered coating. A more preferred lower limit is 10 parts by weight and an upper limit is 100 parts by weight.

The flame-retardant resin composition of the present invention preferably contains a flame-retardant aid in order to further improve flame retardancy.
The flame retardant aid is not particularly limited, and examples thereof include metal oxides, silicone oils, and silicone / acrylic composite rubbers. Of these, metal oxides are preferably used. The metal oxide is not particularly limited, and examples thereof include copper (I) oxide, copper (II) oxide, magnesium oxide, calcium oxide, titanium dioxide, zirconium dioxide, chromium (II) oxide, chromium (III) oxide, and oxidation. Chromium (VI), aluminum oxide, antimony (III) oxide, antimony (V) oxide, yttrium (III) oxide, indium (I) oxide, indium (II) oxide, indium (III) oxide, potassium oxide,
Silver (I) oxide, silver (II) oxide, germanium oxide (I
I), germanium (IV) oxide, cobalt oxide (I
I), cobalt (III) oxide, tin (II) oxide, tin (IV) oxide, cesium oxide, thallium (I) oxide,
Thallium (III) oxide, tungsten (IV) oxide,
Tungsten (VI) oxide, titanium (II) oxide, titanium (III) oxide, titanium (IV) oxide, zinc oxide, iron (II) oxide, iron (III) oxide, barium oxide, manganese (II) oxide, manganese oxide (III), manganese (IV) oxide, manganese (VII) oxide, molybdenum (IV) oxide, molybdenum (VI) oxide, lithium oxide,
Examples thereof include ruthenium (IV) oxide and ruthenium (VII) oxide. These metal oxides may be used alone or in combination of two or more.

The above metal oxide acts as a catalyst for promoting the formation of an organic non-combustible coating when the flame-retardant resin composition of the present invention burns, and forms a stronger organic non-combustible coating. The flame-retardant resin composition has a function of exhibiting high flame retardancy.

The lower limit of the content of the flame retardant aid is 100 parts by weight of the thermoplastic resin, 0.1 to 20 parts by weight of the layered silicate, and 1 to 150 parts by weight of the halogen-free flame retardant. 0.1 part by weight, and the upper limit is 20 parts by weight, relative to 100 parts by weight of the flame-retardant resin composition. If it is less than 0.1 part by weight, a sufficient flame retardant aid effect may not be exhibited. When it exceeds 20 parts by weight, the flame retardancy is further improved, but physical properties such as a decrease in mechanical strength, an increase in specific gravity and lack of flexibility are caused, and the formation of a layered silicate sintered coating is hindered. It may be done.

The method for producing the flame-retardant resin composition of the present invention is not particularly limited, and examples thereof include a method of directly blending and mixing a predetermined amount of a thermoplastic resin, a layered silicate and a non-halogen flame retardant, and heat. A masterbatch is prepared by mixing and mixing a layered silicate in a predetermined amount or more with a plastic resin, and a thermoplastic resin and a non-halogen flame retardant are added so that the prepared masterbatch has a predetermined amount. A so-called masterbatch method for diluting can be used.

The flame-retardant resin composition of the present invention comprises ASTM E
50kW / m in combustion test according to 1354
It is preferred yield stress at the time of the combustion residues is burned with compressed at a rate 0.1 cm / s by heating for 30 minutes at ² radiant heating conditions is not less than 4.9 kPa.
When it is less than 4.9 kPa, the combustion residue is likely to be collapsed by a slight force, and the flame retardancy and fire spread prevention may be insufficient. More preferably, it is 15.0 kPa or more. In order for the flame-retardant resin composition of the present invention to fully exhibit its function as a flame-retardant coating, it is preferable that the sintered body retains its shape until the end of combustion.

[0043]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

(Example 1) Small extruder T manufactured by Japan Steel Works, Ltd.
In EX30, 84.6 parts by weight of polypropylene resin (EA9, manufactured by Nippon Polychem), ethylene-vinyl acetate copolymer (manufactured by Mitsui DuPont, EVA Flex EVA E)
V360) 7.7 parts by weight, magnesium hydroxide (manufactured by Kyowa Chemical Industry Co., Ltd., Kisuma 5J) 40 parts by weight, and swellable fluoromica organically treated with distearyl dimethyl quaternary ammonium salt (Somasif manufactured by Corp Chemical) MAE-
100) 7.7 parts by weight are fed and the set temperature is 190 ° C.
Was melt-kneaded in, and the extruded strand was pelletized by a pelletizer. The obtained pellets were molded into a plate-like material by a hot press at 190 ° C. to obtain a sample for evaluation.

Example 2 In place of 7.7 parts by weight of swellable fluoromica (Somasif MAE-100 manufactured by Coop Chemical Co.) organically treated with distearyldimethyl quaternary ammonium salt, distearyldimethyl quaternary ammonium was used. Montmorillonite organically treated with salt (manufactured by Toyoshun Mining Co.,
A sample for evaluation was prepared in the same manner as in Example 1 except that 7.7 parts by weight of New Sven D) was used.

Example 3 Ammonium polyphosphate coated with melamine resin (Clar) was used in place of 40 parts by weight of magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., Kisuma 5J).
An evaluation sample was prepared in the same manner as in Example 1 except that 40 parts by weight of Exolit AP462, manufactured by iant Inc. was used.

Example 4 As Example 1 except that 40 parts by weight of melamine cyanurate (manufactured by Nissan Chemical Co., Ltd.) was used in place of 40 parts by weight of magnesium hydroxide (manufactured by Kyowa Chemical Industry Co., Ltd., Kisuma 5J). Similarly, a sample for evaluation was prepared.

Example 5 Magnesium hydroxide (Kyowa Chemical Industry Co., Kisuma 5J) was added in an amount of 100 parts by weight, and titanium dioxide (Rutile STR-60C-LP manufactured by Sakai Chemical Co., Ltd.) was used as a flame retardant aid. ) Was added in the same manner as in Example 1 except that 3 parts by weight) was added.

Example 6 Magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., Kisuma 5J) was added in an amount of 100 parts by weight, and zinc oxide (Sakai Chemical Co., FINEX) was used as a flame retardant aid.
A sample for evaluation was prepared in the same manner as in Example 1 except that 3 parts by weight of (-50 LP) was added.

(Comparative Example 1) Small extruder T manufactured by Japan Steel Works, Ltd.
In EX30, 87.3 parts by weight of polypropylene resin (EA9, manufactured by Nippon Polychem), ethylene-vinyl acetate copolymer (manufactured by Mitsui DuPont, EVAflex EVA E
V360) 7.7 parts by weight, magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., Kisuma 5J) 40 parts by weight, and talc (Nippon Talc Co., Ltd., Microace P-6) 5 parts by weight are fed to set temperature 190. The mixture was melt-kneaded at 0 ° C, and the extruded strand was pelletized with a pelletizer. The obtained pellets were molded into a plate-like material by a hot press at 190 ° C. to obtain a sample for evaluation.

Comparative Example 2 Ethylene-Vinyl Acetate Copolymer (Eva Flex EVA EV3 manufactured by Du Pont Mitsui)
60) A test sample was prepared in the same manner as in Example 1 except that 7.7 parts by weight of maleic anhydride-modified propylene oligomer (Sanyo Kasei Co., Ltd., Umex 1001) was used instead of 7.7 parts by weight. did.

(Comparative Example 3) Small extruder T manufactured by Japan Steel Works, Ltd.
In EX30, 87.3 parts by weight of polypropylene resin (EA9, manufactured by Nippon Polychem), ethylene-vinyl acetate copolymer (manufactured by Mitsui DuPont, EVAflex EVA E
V360) 7.7 parts by weight, ammonium polyphosphate coated with melamine resin (Clariant, Exol
40 parts by weight of it AP462) and 5 parts by weight of talc (manufactured by Nippon Talc Co., Ltd., Microace P-6) were melted and kneaded at a set temperature of 190 ° C., and the extruded strand was pelletized by a pelletizer. . The obtained pellets were molded into a plate-like material by a hot press at 190 ° C. to obtain a sample for evaluation.

(Comparative Example 4) Small extruder T manufactured by Japan Steel Works, Ltd.
In EX30, 87.3 parts by weight of polypropylene resin (EA9, manufactured by Nippon Polychem), ethylene-vinyl acetate copolymer (manufactured by Mitsui DuPont, EVAflex EVA E
V360) 7.7 parts by weight, melamine cyanurate (manufactured by Nissan Chemical Co., Ltd.) 40 parts by weight, and talc (manufactured by Nippon Talc Co., Ltd., Microace P-6) 5 parts by weight are fed and melted at a set temperature of 190 ° C. The kneaded and extruded strands were pelletized with a pelletizer. The obtained pellets were molded into a plate-like material by a hot press at 190 ° C. to obtain a sample for evaluation.

(Comparative Example 5) Ethylene-vinyl acetate copolymer (Evaflex EVA EV3, manufactured by Mitsui DuPont)
60) A sample for evaluation was prepared in the same manner as in Example 5 except that 7.7 parts by weight of maleic anhydride-modified propylene oligomer (manufactured by Sanyo Kasei Co., Ltd., Umex 1001) was used instead of 7.7 parts by weight. did.

Comparative Example 6 Ethylene-vinyl acetate copolymer (Evaflex EVA EV3 manufactured by Mitsui DuPont)
60) Instead of 7.7 parts by weight, maleic anhydride-modified propylene oligomer (manufactured by Sanyo Chemical Industry Co., Ltd., Yumex 1)
A sample for evaluation was prepared in the same manner as in Example 6 except that 7.7 parts by weight of (001) was used.

<Evaluation> The following evaluations were performed using the evaluation samples prepared in Examples 1, 2, 3, 4, 5, and 6 and Comparative Examples 1, 2, 3, 4, 5, and 6. The results are shown in Tables 1 and 2. (1) A dispersion state evaluation sample of layered silicate or talc was cut out with a diamond cutter, and a transmission electron microscope (JEM-1200EX manufactured by JEOL Ltd.) was used.
II) The state of dispersion of the layered silicate or talc in the composite was observed by a photograph.

(2) Maximum heat release rate and combustion residue strength measurement Combustion test In accordance with ASTM E 1354 "Combustibility test method for building materials", a test piece (100 mm x 100 mm
× 3mm thickness) 50k by corn calorimeter
Irradiate with heat rays of w / m ² to burn and generate maximum heat generation rate (k
W / m ² ) was determined. In addition, the residue produced after combustion was observed, and the compression rate was 0.1 cm using a strength measuring device.
The stress at yield was measured under the condition of / s.

(3) UL standard burning test In accordance with the UL-94V vertical burning test method, the test piece (1
The flammability (◯: burning time within 10 seconds, ×: burnt out) of 2.7 mm × 127.0 mm × 3.2 mm thickness) was measured.

[0059]

[Table 1]

[0060]

[Table 2]

From Table 1, in the evaluation samples prepared in Examples 1, 2, 3 and 4, the layered silicate in the resin was dispersed in a state where a plurality of playing cards were slightly overlaid and overlapped. The maximum heat generation rate was small, the residue after burning retained its shape, and the stress at its yield point was high. on the other hand,
In the evaluation samples produced in Comparative Examples 1, 3, and 4, talc was dispersed as agglomerates of several μm, and thus sufficient flame retardancy was not obtained. In the evaluation sample prepared in Comparative Example 2, since the layered crystals of the layered silicate were dispersed in a single layer, the layered silicate was dispersed in a state in which a plurality of playing cards were slightly displaced and overlapped. Example 1,
The flame retardancy as much as the evaluation samples prepared in Nos. 2, 3, and 4 was not obtained.

From Table 2, the evaluation samples prepared in Examples 5 and 6 were self-extinguishing within 10 seconds after the flame contact because the layered silicate was dispersed in the resin in a trump shape. On the other hand, the evaluation samples prepared in Comparative Examples 5 and 6 were completely burned because the layered crystals of the layered silicate were dispersed in a single layer.

[0063]

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a flame-retardant resin composition which is excellent in flame retardancy, exhibits a flame-retardant effect due to the shape-retaining effect during combustion, and is also excellent in mechanical strength and thermal properties. be able to.

[Brief description of drawings]

FIG. 1 is a schematic view showing a crystal of a layered silicate.

FIG. 2 is a schematic diagram showing a state in which a layered silicate is dispersed in a trump shape.

FIG. 3 is a schematic diagram showing a state in which a layered silicate is dispersed in a state where a single layer of a layered crystal is peeled off.

[Explanation of symbols]

1 Layered silicate surface 2 Layered silicate side surface 3 Apparent thickness 4 Apparent length 5 thickness 6 length

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 7/00 C08K 7/00 C08L 23/00 C08L 23/00 F term (reference) 4J002 AA001 BB061 BB121 DA057 DE058 DE077 DE087 DE088 DE098 DE118 DE128 DE138 DE147 DE148 DE187 DG057 DH057 DJ006 DJ056 EU187 EU197 EW047 EW127 EW147 FA016 FD137 FD138

Claims (8)

[Claims] 1. A thermoplastic resin of 100 parts by weight, a layered silicate of 0.1 to 20 parts by weight, and a halogen-free flame retardant of 1-1.
A flame-retardant resin composition containing 50 parts by weight, wherein the layered silicate has an apparent thickness of 5 because at least a part of the monolayers of the layered crystals are overlapped by shifting the centers of the monolayer surfaces. A flame-retardant resin composition having a flat plate shape of -50 nm and a length of 500 nm or more and dispersed. 2. A flame-retardant resin composition comprising 0.1 to 20 parts by weight of a flame-retardant aid with respect to 100 parts by weight of the flame-retardant resin composition according to claim 1. 3. In a combustion test according to ASTM E 1354, 30 under a radiant heating condition of 50 kW / m ^2.
The rate of combustion residue of the combustion residue burned by heating for 0.
The flame-retardant resin composition according to claim 1 or 2, wherein the yield point stress when compressed at 1 cm / s is 4.9 kPa or more. 4. The flame-retardant resin composition according to claim 1, 2 or 3, wherein the thermoplastic resin is a polyolefin resin. 5. The non-halogen flame retardant is a phosphorus compound,
The flame-retardant resin composition according to claim 1, which is at least one compound selected from the group consisting of a metal hydroxide and a melamine derivative. 6. The flame-retardant resin composition according to claim 2, 3, 4 or 5, wherein the flame-retardant aid is a metal oxide. 7. The layered silicate is montmorillonite and / or
Or a swelling mica,
The flame-retardant resin composition according to 2, 3, 4, 5 or 6. 8. The flame-retardant resin composition according to claim 1, wherein the layered silicate contains an alkylammonium ion having 6 or more carbon atoms.