JP3635567B2 - Polyolefin resin composition - Google Patents

Description

【０１４３】
【表２】

【０１４４】
＊実施例５、８、９、１２、１４〜１９、２４、２５、３０、３１、３３については自己消火性が確認できた。
表１及び表２から明らかなように、実施例１〜実施例３６の本発明のポリオレフィン系樹脂組成物からなる評価用サンプルは、いずれも燃焼時に層状珪酸塩により焼結体が形成され、燃焼残渣の形状が保持されていると共に、該燃焼残渣は０．１ｃｍ／ｓで圧縮した時に降伏点を有し、且つ、降伏点応力が４．９×１０^３Ｐａ以上であった。これにより燃焼後も形状崩壊が起こらず、自己消火性に優れ、延焼の起こらない優れた難燃性を有するものであった。また、破断時伸度も全て７５０％以上であり、柔軟性にも優れていた。
【０１４５】
これに対し、表２から明らかなように、層状珪酸塩を含有させなかった比較例１〜比較例３、及び、比較例６及び比較例７のポリオレフィン系樹脂組成物からなる評価用サンプルは、燃焼残渣が生成していないか又は燃焼残渣の形状が保持されていなかったので、自己消火性が悪く、難燃性が劣っていた。また、層状珪酸塩の平均層間距離が３ｎｍ未満であった比較例４のポリオレフィン系樹脂組成物からなる評価用サンプルは、自己消火性が悪く、難燃性が劣っていた。
【０１４６】
また、比較例５では、層間距離は３．５ｎｍであるものの、５層以下に分散している層状珪酸塩が存在していないことが考えられ、難燃性に大きな影響を及ぼさなかった。燃焼被膜形成においても局所的な形成にとどまり、強度も保持できていなかった。
【０１４７】
【発明の効果】
本発明は、上述の構成よりなるので、燃焼時に層状珪酸塩による焼結体が形成され、燃焼残渣の形状が保持される。これにより、燃焼後も形状崩壊が起こらず、形状保持性、自己消火性に優れ、延焼の起こらない、優れた難燃性を有し、更に、機械的強度にも優れ、透明性も保持されるポリオレフィン系樹脂組成物を提供することができる。また、本発明によれば、ポリオレフィン系樹脂の弾性率やガスバリア性といった物性を著しく改良することができると共に、分子鎖の拘束による熱変形温度の上昇に基づく耐熱性や、無機結晶による核剤効果に基づく寸法安定性等の諸物性についても大幅な向上が可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyolefin resin composition that exhibits excellent flame retardancy, a thermoplastic resin for covering or sheathing an electric wire using the same, and an insulated wire.
[0002]
[Prior art]
In recent years, polyolefin resins have attracted attention as environmentally friendly materials due to the problem of waste plastic treatment and environmental hormones. Specifically, polyethylene-based resins and polypropylene-based resins have been studied as alternative materials for polyvinyl chloride-based resins.
[0003]
However, since polyolefin resin is nonpolar, it is very difficult to develop functions such as printability, adhesiveness, and flame retardancy. In particular, since polyolefin resins are one of the most flammable resins, it is the most difficult task to develop flame retardancy. Currently, halogen-containing flame retardants are kneaded into polyolefin resins. There are many examples of dealing with this.
[0004]
Halogen-containing flame retardants are highly flame retardant and have relatively little reduction in moldability and mechanical strength of molded products. However, when they are used, a large amount of halogen-based gas is required during molding and combustion. Since the generated gas corrodes the equipment and there are concerns about the effects on the human body, so-called non-halogen flame retardant treatment methods that do not use halogen-containing compounds are highly desirable from the viewpoint of safety. It is rare.
[0005]
As one of non-halogen flame retardant technologies for polyolefin resins, there is a method of adding a metal compound such as aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate or the like that does not generate toxic gas during combustion to polyolefin resins. This is disclosed in Japanese Patent Application Laid-Open No. 57-165437 and Japanese Patent Application Laid-Open No. 61-36343.
[0006]
However, in order to impart sufficient flame retardancy to the flammable polyolefin resin, it is necessary to add a large amount of the above metal compound, as a result, the mechanical strength of the resulting molded product is significantly reduced, There is a problem that it is difficult to put to practical use.
[0007]
Among the above metal compounds, when a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is added to the polyolefin resin, a coating layer cannot be formed during combustion, and a brittle ash is exposed, and the residue However, there is a problem that the fire spread due to the deformation of the material cannot be stopped in addition to losing the function as a heat insulating layer at an early stage.
[0008]
In addition, a method has been proposed in which a flame retardant is expressed by adding a phosphorus flame retardant to a polyolefin resin and utilizing the oxygen barrier effect due to the formation of a surface film during combustion. 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 product is significantly reduced. There is a problem that it is difficult to put to practical use.
[0009]
When the phosphorus-based flame retardant is added to the polyolefin-based resin, although a film is locally formed, a strong film layer cannot be formed as a continuous layer. In addition, the mechanical strength of the locally formed film is very weak, and during combustion, brittle ash is exposed and the residue falls off. There is a problem that the spread of fire due to deformation cannot be stopped.
[0010]
JP-A-6-2470 discloses a resin composition in which red phosphorus or a phosphorus compound and expandable graphite are added to a polyolefin resin. Although this resin composition has sufficient flame retardancy when viewed from the oxygen index, it can form a film only locally and cannot form a strong film layer as a continuous layer. In addition, the mechanical strength of the local coating is very weak, and during combustion, brittle ash is exposed and the residues fall off. There is a problem that cannot be stopped.
[0011]
For this reason, for example, when the polyolefin-based resin is used as a wall lining material as a flame retardant material molded into a sheet shape, the temperature of the back surface when the surface is heated to 1000 ° C. is suppressed to 260 ° C. or less. Not only does it fail to meet the standards of fire test, but also fire resistance is insufficient, and only the brittle ash remains in the fire test and fire test, and the residue drops off. There is a problem.
[0012]
[Problems to be solved by the invention]
In view of the above, the present invention is a polyolefin-based resin composition that is excellent in flame retardancy, particularly exhibits excellent flame retardancy due to the shape retention effect during combustion, and also has excellent mechanical strength and thermal characteristics, An object of the present invention is to provide a thermoplastic resin for sheathing or sheathing an electric wire and an insulated wire.
[0013]
[Means for Solving the Problems]
The present invention is a polyolefin resin composition comprising 100 parts by weight of a polyolefin resin and 0.1 to 100 parts by weight of a layered silicate, 50 kW / m ² Yield point stress when the combustion residue obtained by heating and burning for 30 minutes under the heating conditions of 0.1 cm / s is 4.9 × 10 ³ It is a polyolefin resin composition which is Pa or more.
The present invention is described in detail below.
[0014]
The polyolefin resin composition of the present invention comprises 100 parts by weight of polyolefin resin and 0.1 to 100 parts by weight of layered silicate.
The polyolefin resin used in the present invention is obtained by polymerizing an olefin monomer having a polymerizable double bond.
[0015]
The olefinic monomer is not particularly limited, and examples thereof include α- such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene. Examples thereof include olefins and conjugated dienes such as butadiene and isoprene. These olefinic monomers may be used alone or in combination of two or more.
[0016]
The polyolefin resin is not particularly limited. For example, a homopolymer of ethylene, a copolymer of ethylene and α-olefin, a copolymer of ethylene and (meth) acrylic acid, ethylene and (meth) acrylic acid. Copolymer with ester, copolymer of ethylene and vinyl acetate, homopolymer of propylene, copolymer of propylene and α-olefin, random copolymer or block copolymer of propylene and ethylene, butene And homopolymers or copolymers of conjugated dienes such as butadiene and isoprene. These polyolefin resin may be used independently and 2 or more types may be used together. In addition, in this specification, (meth) acryl means acryl or methacryl.
[0017]
Among the polyolefin resins, ethylene homopolymers, propylene homopolymers, copolymers of ethylene or propylene and α-olefins copolymerizable therewith, copolymers of ethylene and (meth) acrylic acid esters. A polymer or a copolymer of ethylene and vinyl acetate is preferably used. These polyolefin resin may be used independently and 2 or more types may be used together.
[0018]
The molecular weight and molecular weight distribution of the polyolefin resin are not particularly limited, but the weight average molecular weight is preferably 5,000 to 5,000,000, more preferably 20,000 to 300,000, and the molecular weight distribution (weight average molecular weight / number average). The molecular weight is preferably 1.1 to 80, more preferably 1.5 to 40.
The layered silicate used in the present invention is a silicate mineral having an exchangeable cation in the crystal structure including the interlayer.
[0019]
The layered silicate is not particularly limited, and examples thereof include smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite; vermiculite, halloysite, swellable mica, and the like. Montmorillonite and swellable mica are preferably used. These layered silicates may be used independently and 2 or more types may be used together.
The layered silicate may be a natural product or a synthetic product.
[0020]
As the layered silicate, a smectite clay mineral or swellable mica having a large shape anisotropy effect defined by the following formula (1) is used. It is more preferable from the viewpoint of improving the properties.
Shape anisotropy effect = area of crystal surface (a) / area of crystal surface (b) (1)
Although it does not specifically limit as a cation exchange capacity | capacitance of the said layered silicate, It is preferable that it is 50-200 milliequivalent / 100g. When the amount is less than 50 mm equivalent / 100 g, the amount of the cationic surfactant intercalated between the crystal layers by ion exchange decreases, so that the layers may not be sufficiently nonpolarized, whereas 200 mm When the equivalent amount / 100 g is exceeded, the bonding strength between the layers of the layered silicate becomes strong, and the crystal flakes may be difficult to peel off.
[0021]
The exchangeable cation is not particularly limited, and examples thereof include monovalent metal ions such as sodium and potassium.
When exchanging exchangeable cations with other metal ions, it is preferable to exchange with metal ions having an effect of improving the acidity of the layered silicate from before ion exchange by ion exchange. When the acidity of the layered silicate is improved, the reactivity with the polyolefin resin and the additive added to the polyolefin resin is easily improved, and the dispersibility of the layered silicate is improved.
[0022]
In the layered silicate used in the present invention, the exchangeable cation in the crystal structure is preferably ion-exchanged with a divalent metal ion. When ion exchange is performed with metal ions exceeding divalent, the interlayer bonding force of the layered silicate becomes strong, and delamination may not proceed.
[0023]
It does not specifically limit as said divalent metal ion, For example, nickel, magnesium, calcium etc. are mentioned. The effect of improving the acidity of the layered silicate by ion exchange with these metal ions increases in the order of nickel, magnesium and calcium.
[0024]
The ion exchange with divalent metal ions such as nickel, magnesium, calcium and the like improves the acidity of the hydroxyl group of the lamellar silicate crystal flakes as described in, for example, “Cray Materials” (1997, 32, p645 to 651). Among the divalent metal ions, nickel ions and magnesium ions are preferable because the bonding force between crystal flakes during sintering is improved and a strong sintered film can be easily formed.
[0025]
The layered silicate used in the present invention preferably contains a cationic surfactant in its crystal structure. Examples of the method for containing a cationic surfactant in the crystal structure of the layered silicate include, for example, a part of or all of the metal ions present as exchangeable cations in the crystal structure of the layered silicate. The method of exchanging is mentioned.
The cationic surfactant is not particularly limited, and examples thereof include quaternary ammonium salts and quaternary phosphonium salts.
[0026]
The quaternary ammonium salt is not particularly limited, and examples thereof include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl ammonium salt, distearyl dimethyl ammonium salt, di-cured tallow dimethyl ammonium salt, and distearyl dibenzyl ammonium salt. Examples include (co) polymers having a quaternary ammonium salt structure. These quaternary ammonium salts may be used independently and 2 or more types may be used together. In the present specification, the (co) polymer means a polymer or a copolymer.
[0027]
The (co) polymer having the quaternary ammonium salt structure is not particularly limited. For example, homopolymers of (meth) acrylic monomers having an amino group, an alkylamino group, a dialkylamino group, and the like ( It can be obtained by quaternary ammonium chlorination of a copolymer of a (meth) acrylic monomer with another (meth) acrylic monomer and / or a styrene monomer such as styrene, α-methylstyrene, vinyltoluene or the like with hydrochloric acid or the like. (Co) polymer is mentioned. These (co) polymers having a quaternary ammonium salt structure may be used alone or in combination of two or more.
[0028]
As the cationic surfactant, if a (co) polymer having a high oxygen content or a (co) polymer having an aromatic ring such as styrene is used, the formation of an organic incombustible film is promoted, and thus flame retardant Improves. In addition, when metal ions contained as exchangeable cations between layers of the above layered silicate are exchanged with a long chain (co) polymer, the layered silicate is easy to peel and disperse, and uniform inorganic sintering during combustion Since a film is formed, flame retardancy is improved.
[0029]
The quaternary phosphonium salt is not particularly limited. For example, dodecyltriphenylphosphonium salt (DTPB), methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, trioctylphosphonium salt, distearyldimethylphosphonium salt, Distearyl benzyl phosphonium salt etc. are mentioned. These quaternary phosphonium salts may be used alone or in combination of two or more.
[0030]
By using a quaternary phosphonium salt as the cationic surfactant, the intercalant can be easily fixed between the layers of the layered silicate during combustion, and the effect of improving flame retardancy is increased. This is because the quaternary phosphonium salt itself has higher flame retardancy than the quaternary ammonium salt and other intercalants.
[0031]
In addition, since the quaternary phosphonium salt contains phosphorus, a surface film is formed at the time of combustion and exhibits an oxygen blocking effect, similarly to the function of the phosphorus compound described later. In this case, the phosphorus component is present in the vicinity of the crystal flake of the layered silicate as compared with the case where the phosphorus compound is added alone to the polyolefin resin as a flame retardant. Due to the action, more effective film formation is performed.
[0032]
Among the quaternary phosphonium salts, quaternary alkylphosphonium salts having an alkyl group having 6 or more carbon atoms are preferably used. When the alkyl group has less than 6 carbon atoms, the hydrophilicity of the alkylphosphonium ion becomes strong, and the interlayer of the layered silicate may not be sufficiently nonpolarized.
[0033]
The layered silicate used in the present invention has a (001) plane average interlayer distance of 3 nm or more measured by wide-angle X-ray diffraction measurement, and is dispersed in a polyolefin resin composition in a state of 5 layers or less. It is preferable to include.
The number and ratio of the layered silicate can be calculated by transmission electron microscope photography.
[0034]
The average interlayer distance of the layered silicate is an average interlayer distance in the case where fine flaky crystals are used as a layer, and is calculated by X-ray diffraction peak and transmission electron microscope photography, that is, by a wide-angle X-ray diffraction measurement method. It can be done.
[0035]
When the average interlayer distance is 3 nm or more, the polyolefin-based resin easily enters between the layers of the layered silicate, so that the layered silicate crystal flake layers are separated so as to have 5 layers or less, and the interface area increases. . The fact that the interlayer is cleaved to 3 nm or more means that the layered silicate is easy to disperse during combustion or the like, and the state in which it is dispersed to 5 or less layers weakens the interaction between the layers. This means that a part of the layered silicate laminate is dispersed. Therefore, when the layered silicate has an average interlayer distance of 3 nm or more and includes those dispersed in 5 layers or less in the polyolefin resin composition, the polyolefin resin composition of the present invention has flame retardancy, Functions such as mechanical strength and gas barrier properties are easily developed.
[0036]
The average interlayer distance is more preferably 6 nm or more. When the average interlaminar distance is 6 nm or more, the lamellar silicate crystal flake layers are separated for each layer, and the interaction between the lamellar silicate crystal flake layers is weakened to an almost negligible level. The layered state of the flakes in the polyolefin-based resin proceeds in the direction of destabilization and stabilization.
[0037]
When the layered silicate forming a large number of layers in the crystalline state is delaminated, the number of crystal flakes and the interface area of the layered silicate increase, and the distance between the crystal flakes decreases, so that the layered silicate during combustion It is considered that the sintered body is easily formed by the movement of the salt crystal flakes.
[0038]
In the layered silicate used in the present invention, 10% by weight or more of the total layered silicate is preferably dispersed in 5 layers or less. More preferably, it is 20% by weight or more. Moreover, if it is dispersed in 5 layers or less, the effect as described above can be obtained, but if it is divided in 3 layers or less, it is more effective and preferable. Further, it is preferable that the isolated layer is sliced as an effective layered state.
[0039]
That is, when the layered silicate has an average interlayer distance of 3 nm or more and includes those dispersed in 5 or less layers in the polyolefin resin composition, the polyolefin resin composition of the present invention can be a flame retardant coating. It becomes easy to form a sintered body. Since this sintered body is formed at an earlier stage during combustion as the dispersion progresses, not only the supply of oxygen from the outside but also the combustible gas generated by the combustion can be shut off. Incombustibility is exhibited.
[0040]
The layered silicate used in the present invention may be treated with a compound having a functional group that can be chemically bonded to a hydroxyl group on the end face or has chemical affinity.
The functional group capable of being chemically bonded to the hydroxyl group or having chemical affinity is not particularly limited, and examples thereof include hydroxyl groups such as an alkoxyl group, an epoxy group, a carboxyl group, a hydroxyl group, a maleic anhydride group, an isocyanate group, and an aldehyde group. A functional group having a high chemical affinity.
[0041]
The compound having a functional group capable of being chemically bonded to the hydroxyl group or having chemical affinity is not particularly limited, and examples thereof include silane compounds, titanate compounds, glycidyl compounds, carboxylic acids, and alcohols containing the various functional groups described above. Among them, silane compounds are preferably used. These compounds may be used independently and 2 or more types may be used together.
[0042]
The silane compound is not particularly limited, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-amino. Propyldimethylmethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyldimethylethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, hexyltrimethoxysilane, hexyltri Ethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-amino Propylmethyldimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltri An ethoxysilane etc. are mentioned. These silane compounds may be used alone or in combination of two or more.
[0043]
The amount of the layered silicate added is 0.1 to 100 parts by weight with respect to 100 parts by weight of the polyolefin resin. If the amount is less than 0.1 parts by weight, it becomes difficult to form a sintered body, and the flame retardancy of the resulting polyolefin-based resin composition and molded body becomes insufficient. The specific gravity of the polyolefin resin composition and the molded product to be obtained is increased, and the practicality is impaired. Preferably it is 5-100 weight part.
[0044]
Examples of a method for dispersing the layered silicate in the polyolefin-based resin include, for example, (1) a method of using a layered silicate subjected to an organic treatment, and (2) dispersion by foaming in the presence of the layered silicate. Methods and the like. Said method (1) and method (2) may be used independently, respectively, and both may be used together. By using these dispersion methods, the layered silicate can be more uniformly and finely dispersed in the polyolefin resin.
[0045]
Examples of the method for organizing the (1) layered silicate include, for example, (1-1) a metal ion which is contained as an exchangeable cation in the crystal structure of the layered silicate by the cationic surfactant. Method of exchanging, (1-2) A hydroxyl group present on the crystal surface of the layered silicate can be chemically bonded to the hydroxyl group or has a chemical affinity and / or a reactive functional group at the molecular end. (1-3) a layered silicate crystal surface, an agent having an anionic surface active ability, and / or an anionic surface active ability, and in a molecular chain And a method of chemically modifying with a reagent having one or more reactive functional groups in addition to the anion moiety. These methods may be used independently and 2 or more types may be used together.
[0046]
As a method of dispersing by foaming in the presence of (2) layered silicate, for example, (2-1) a composition comprising 100 parts by weight of polyolefin-based resin and 0.1 to 100 parts by weight of layered silicate On the other hand, a method in which a gaseous compound is impregnated at normal temperature and pressure under high pressure, and then the gaseous compound is vaporized in the composition to form a foam, and (2-2) layered silicic acid. Examples thereof include a method in which a pyrolytic foaming agent is previously contained between salt layers, and the thermal decomposable foaming agent is dispersed by heating to decompose to form a foamed structure. These methods may be used independently and 2 or more types may be used together.
[0047]
The more the layered silicate peels between the layers and the crystal flakes are dispersed in the polyolefin resin, the smaller the average distance between the crystal flakes, and the sintered body due to the movement of the layered silicate crystal flakes during combustion Becomes easier to form. Further, as the layered silicate crystal flakes are dispersed, the elastic modulus and gas barrier properties of the polyolefin resin-layered silicate composite material are remarkably improved.
[0048]
Any of the above phenomena is due to an increase in the interfacial area between the layered silicate and the polyolefin resin as the degree of dispersion of the crystal flakes increases. That is, the molecular motion of the polyolefin resin is constrained on the adhesive surface between the polyolefin resin and the layered silicate, thereby increasing the mechanical strength such as the elastic modulus of the polyolefin resin. The better, the more efficiently the mechanical strength of the polyolefin resin can be increased.
[0049]
In addition, gas molecules in the polymer are much easier to diffuse than inorganic materials, so when gas molecules diffuse in the composite material, they diffuse while bypassing the inorganic material. Accordingly, also in the present invention, the gas barrier property of the polyolefin-based resin can be more efficiently increased as the degree of dispersion of the lamellar silicate crystal flakes increases.
[0050]
The polyolefin resin composition of the present invention is 50 kW / m ² Yield point stress is 4.9 × 10 when the combustion residue obtained by heating and burning for 30 minutes under the above heating conditions is compressed at 0.1 cm / s. ³ Pa or higher.
[0051]
In order for the sintered body of the polyolefin resin composition to exhibit a function as a flame retardant coating, it is necessary for the sintered body to maintain the shape until the end of combustion. If there is no yield point when compressing the combustion residue, the combustion residue collapses with a small force. Even if there is a yield point, the yield point stress is 4.9 × 10 ³ If it is less than Pa, the combustion residue collapses with a very small force. Preferably 1.5 × 10 ⁴ Pa or higher.
[0052]
The polyolefin resin composition of the present invention is 50 kW / m ² The maximum heat generation rate when heated and burned for 30 minutes under the heating conditions of 800 kW / m ² The following is preferable. 800kW / m ² If it exceeds, the fire during combustion is too strong, and it is difficult to suppress the combustion of the polyolefin resin composition. More preferably 400 kW / m ² It is as follows.
[0053]
The polyolefin resin composition of the present invention preferably further contains a phosphorus compound, a metal hydroxide, or a melamine derivative in order to improve flame retardancy. The phosphorus compound, metal hydroxide and melamine derivative may be used alone or in combination of two or more.
[0054]
The phosphorus compound is not particularly limited, and examples thereof include red phosphorus, ammonium polyphosphate, and a phosphorus compound represented by the following general formula (1). Among these, phosphorus compounds represented by the following general formula (1) are preferably used. These phosphorus compounds may be used alone or in combination of two or more.
R ³ (R ² ) (OR ¹ ) P = O (1)
Where R ¹ And R ³ Represents 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, an alkoxyl group, an aryl group or an aryloxy group; ¹ , R ² And R ³ May be the same or different. If the number of carbon atoms exceeds 16, the relative content of phosphorus will be low, and the flame retardancy imparting effect may be insufficient.
[0055]
The red phosphorus is preferably one whose surface is coated with a resin in order to improve moisture resistance or to prevent spontaneous ignition when added to a polyolefin resin and kneaded.
The ammonium polyphosphate may be subjected to surface treatment such as melamine modification.
[0056]
The phosphorus compound represented by the general 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-propylphosphone. Acid, t-butylphosphonic acid, 2,3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphine Examples include acids, phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, bis (4-methoxyphenyl) phosphinic acid and the like. These phosphorus compounds may be used alone or in combination of two or more.
[0057]
The amount of the phosphorus compound added is preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the polyolefin resin. If the amount is less than 0.5 parts by weight, a sufficient flame retardancy improving effect may not be obtained. On the other hand, if the amount exceeds 100 parts by weight, the mechanical strength of the molded product obtained from the polyolefin resin composition decreases. There are things to do. More preferably, it is 2 to 50 parts by weight.
[0058]
The metal hydroxide is not particularly limited, and examples thereof include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, dosonite, calcium aluminate, and dihydrate gypsum. Among them, magnesium hydroxide and hydroxide Aluminum is 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 and dehydration reaction at different temperatures, so that a higher flame retardancy imparting effect can be obtained.
[0059]
Further, the metal hydroxide may be subjected to a surface treatment with a surface treatment agent. The surface treatment agent is not particularly limited. For example, silane coupling agents, titanate coupling agents, aluminum coupling agents, polyvinyl alcohol surface treatment agents, epoxy surface treatment agents, higher fatty acid surface treatment agents. Etc. These surface treatment agents may be used alone or in combination of two or more.
[0060]
The addition amount of the metal hydroxide is preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the polyolefin resin. When the amount is less than 0.5 parts by weight, the sufficient effect of improving flame retardancy may not be obtained. On the other hand, when the amount exceeds 100 parts by weight, the flame retardancy is further improved, but the increase in specific gravity and the flexibility. Problems such as lack may occur. More preferably, it is 20-60 weight part.
[0061]
Since the metal hydroxide undergoes an endothermic dehydration reaction under high heat during combustion, it exhibits an effect of extinguishing the fire by lowering the temperature of the combustion field by absorbing water and releasing water molecules. Moreover, since the polyolefin-type resin composition of this invention contains layered silicate, the flame retardance improvement effect by a metal hydroxide is increased more. This is because the flame retardancy improving effect based on the film formation at the time of burning the layered silicate and the flame retardancy improving effect based on the endothermic dehydration reaction of the metal hydroxide occur competitively, and each effect is promoted. It depends.
[0062]
The melamine derivative is not particularly limited, and examples thereof include melamine, melamine cyanurate, melamine isocyanurate, melamine phosphate, and those subjected to surface treatment. These melamine derivatives may be used alone or in combination of two or more. As said surface treatment, the process similar to the process given to a metal hydroxide is mentioned.
[0063]
It is preferable that the addition amount of the said melamine derivative is 0.5-100 weight part with respect to 100 weight part of polyolefin resin. If the amount is less than 0.5 parts by weight, a sufficient effect of improving flame retardancy may not be obtained. On the other hand, if the amount exceeds 100 parts by weight, the physical properties of the polyolefin resin composition of the present invention may be deteriorated or layered. Silicates may be prevented from forming a sintered coating. More preferably, it is 1-30 weight part.
[0064]
The polyolefin resin composition of the present invention preferably further contains a silicate compound other than the above-mentioned layered silicate in order to improve flame retardancy.
The silicate compound is not particularly limited, and examples thereof include calcium silicates such as wollastonite and zonotolite; clay minerals such as talc, activated clay, kaolin clay, sepiolite and imogolite; silica-based balloons and the like. Of these, talc is preferably used because of its affinity with the layered silicate and excellent particle size selectivity. These silicate compounds may be used alone or in combination of two or more.
[0065]
Moreover, as said silicate compound, what has an average particle diameter different from a layered silicate is preferable. By adding a silicate compound having an average particle diameter different from that of the layered silicate to the polyolefin resin composition of the present invention, inorganic components such as the layered silicate and the silicate compound are sintered at the time of combustion. It becomes easy to coat the combustion surface as a body, and it becomes easy to form a strong flame retardant coating.
[0066]
The addition amount of the silicate compound is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the polyolefin resin. If the amount is less than 0.5 parts by weight, a sufficient flame retardancy improving effect may not be obtained. On the other hand, if the amount exceeds 20 parts by weight, the mechanical strength of the molded product obtained from the polyolefin-based resin composition decreases. Or the specific gravity may be too high. More preferably, it is 2 to 10 parts by weight.
[0067]
The polyolefin resin composition of the present invention preferably further contains a metal oxide in order to improve flame retardancy.
The metal oxide is not particularly limited. For example, copper oxide (I), copper oxide (II), magnesium oxide, calcium oxide, titanium dioxide, zirconium dioxide, chromium oxide (II), chromium oxide (III), oxidation Chromium (VI), aluminum oxide, antimony oxide (III), antimony oxide (V), yttrium oxide (III), indium oxide (I), indium oxide (II), indium oxide (III), potassium oxide, silver oxide ( I), silver (II) oxide, germanium (II) oxide, germanium oxide (IV), cobalt (II) oxide, cobalt (III) oxide, tin (II) oxide, tin (IV) oxide, cesium oxide, thallium oxide (I), thallium (III) oxide, tungsten oxide (IV), tungsten oxide (VI), titanium oxide (II), titanium oxide (III), titanium oxide (IV), zinc oxide, iron oxide (II), iron oxide (III), barium oxide, manganese (II) oxide, manganese (III) oxide, manganese oxide ( IV), manganese oxide (VII), molybdenum oxide (IV), molybdenum oxide (VI), lithium oxide, ruthenium oxide (IV), ruthenium oxide (VIII) and the like. These metal oxides may be used alone or in combination of two or more.
[0068]
The metal oxide acts as a catalyst for promoting the formation of an organic incombustible coating when the polyolefin resin composition of the present invention burns, and exhibits a high flame retardancy by forming a stronger organic incombustible coating. It has a function.
[0069]
It is preferable that the addition amount of the said metal oxide is 0.1-10 weight part with respect to 100 weight part of polyolefin resin. If the amount is less than 0.1 parts by weight, a sufficient effect of improving flame retardancy may not be obtained. On the other hand, if the amount exceeds 10 parts by weight, the physical properties of the polyolefin resin composition of the present invention may be deteriorated. . More preferably, it is 0.2-5 weight part.
[0070]
In order to further improve the flame retardancy, the polyolefin resin composition of the present invention has an affinity for the polyolefin resin and the segment (A) block having a functional group showing reactivity to the polyolefin resin. It is preferable to contain the AB type block copolymer which consists of the segment (B) block which has.
The functional group in the segment (A) block is not particularly limited as long as it is a functional group capable of chemically bonding to a hydroxyl group present on the crystal surface of the layered silicate or a functional group having chemical affinity. For example, a carboxyl group, An epoxy group etc. are mentioned.
[0071]
As said segment (A) block, what has many said functional groups in a molecule | numerator is preferable. The molecular weight of the segment (A) block is not particularly limited, but is 1 × 10. ⁴ ~ 5x10 ⁴ It is preferable that 5 × 10 ⁴ If it exceeds 1, the degree of freedom of the segment (A) block is lowered, and the reactivity with the layered silicate may be inhibited.
[0072]
The segment (B) block is preferably of the same type as the polyolefin resin used as the main component in the polyolefin resin composition of the present invention, more preferably the same polyolefin resin.
The molecular weight of the segment (B) block is not particularly limited, but is 1 × 10 ⁴ ~ 5x10 ⁴ It is preferable that 5 × 10 ⁴ If it exceeds 1, the degree of freedom of the segment (B) block is lowered, and a sufficient dispersibility improvement effect may not be obtained.
[0073]
Unlike the ABA type block copolymer, the AB type block copolymer composed of the segment (A) block and the segment (B) block is different from the ABA type block copolymer in that the segment (A ) Since the block and the segment (B) block having affinity for the polyolefin resin are located at both ends, the delamination of the layered silicate can be efficiently promoted, and the layered silicate Dispersibility in the polyolefin resin can be improved.
[0074]
The polyolefin resin composition of the present invention preferably further contains a compound having an aromatic hydroxyl group in order to improve flame retardancy.
The compound having an aromatic hydroxyl group is not particularly limited as long as it can capture radicals, and examples thereof include 2,6-di-t-butyl-p-cresol and 2,6-di-t-butyl. -4-ethylphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy- 3,5-di-t-butylanilino) -1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propione , Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy- Hydroxynamamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl) -4-hydroxybenzyl) benzene, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl) calcium, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate 2,4-bis [(octylthio) methyl] -O-cresol, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3, , 9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} 2,4,8,10-tetraoxysaspiro [ 5,5] Udecane, p-phenylphenol, gallic acid and the like. These compounds having an aromatic hydroxyl group may be used alone or in combination of two or more.
[0075]
The compound having an aromatic hydroxyl group delays the combustion reaction by capturing radicals which are decomposition products in the process where the polyolefin resin is thermally decomposed into a combustible gas under high heat during combustion. Demonstrate the function.
[0076]
The addition amount of the compound having an aromatic hydroxyl group is preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the polyolefin resin. If it is less than 0.01 part by weight, a sufficient flame retardancy improving effect may not be obtained. On the other hand, if it exceeds 30 parts by weight, the physical properties of the polyolefin resin composition may be reduced, or the layered silicate may May inhibit the formation of a sintered coating. More preferably, it is 0.05 to 10 parts by weight.
[0077]
The polyolefin resin composition of the present invention includes, for example, a crystal nucleating agent for oxidizing the polyolefin resin crystal to make the physical properties uniform by oxidizing within the range that does not hinder the achievement of the object of the present invention. Various additives such as an inhibitor, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a lubricant, a processing aid, a flame retardant, and an antistatic agent may be added.
[0078]
The polyolefin resin composition of the present invention can be produced by various methods. It does not specifically limit as a manufacturing method of the polyolefin-type resin composition of this invention, For example, (1) Polyolefin-type resin and layered silicate which are essential components, Said various flame-retardant improvement agents which are preferable to contain, A method of melt-kneading various additives added as necessary with an extruder, a two-roll, a Banbury mixer, etc. (2) Compounding in an organic solvent in which both the polyolefin resin and the layered silicate are dissolved (Mixing), (3) A method of polymerizing and compounding an olefin monomer using a layered silicate containing a transition metal complex.
[0079]
The transition metal complex used in the above method (3) is not particularly limited as long as it can polymerize an olefin monomer, and examples thereof include metal complexes of groups 4, 5, 10, 11 and the like. .
[0080]
The application of the polyolefin resin composition of the present invention is not particularly limited and can be widely used for applications requiring flame retardancy, and examples thereof include electric wire coverings, sheaths, decorative sheets and the like. It is suitably used for coating and sheathing resins. The resin for covering the wire and the sheath is required to have flame retardance in order to prevent the fire from spreading through the wire in the event of a fire (JIS C 3005).
[0081]
A thermoplastic resin comprising the polyolefin resin composition of the present invention and used for covering an electric wire or a sheath is also one aspect of the present invention. Moreover, the insulated wire using the said thermoplastic resin is also one of this invention.
[0082]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In the examples, “part” means “part by weight”.
[0083]
(Example 1)
1. Exchange of metal ions in layered silicates by transition metal complexes.
Montmorillonite (trade name “Bengel A”, manufactured by Toyshun Mining Co., Ltd.) 5 g and distilled water 495 g were put into a beaker, and xylene (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was added to further expand the interlayer distance. The mixture was stirred at room temperature for about 2 hours using a motor stirrer to prepare a montmorillonite swelling slurry. Next, 0.27 g of dicyclopentedienyl titanium dichloride / distearyldimethylammonium was added to the swelling slurry, and the mixture was stirred for 24 hours at room temperature using a motor stirrer. separated. In order to remove the unnecessary component adhering to the solid content, the operation of separating the solid content with a centrifugal separator was further repeated twice after the solid content was dispersed again in distilled water. A composition obtained by vacuum drying the obtained solid content at 50 ° C. for 48 hours using a vacuum dryer was used as an organic layered silicate containing a transition metal complex. Yield was 5.10 g. This was designated as MMT-A.
[0084]
2. Polymerization of ethylene
After replacing the inside of the 300 mL pressure-resistant glass container with argon, 5.00 g of MMT-A, which is a previously prepared transition metal complex-containing organic layered silicate (dicyclopentedienyl titanium dichloride / distearyldimethylammonium-added montmorillonite), was added. And dissolved in 150 mL of toluene. Further, 30 mL of methylalumoxane (10 wt% toluene solution, manufactured by Aldrich) was added dropwise from a syringe over 10 minutes. Next, ethylene gas is introduced into the container, and the inside of the system is 1.1 kg / cm. ² The polymerization was carried out at 0 ° C. for 4 hours. After the reaction, 300 mL of methanol was added to the system to stop the reaction, and the precipitated polymer was recovered to obtain 13.5 g of a layered silicate / polymer composite composition (I).
[0085]
The obtained layered silicate / polymer composite composition (I) was analyzed using a Fourier transform infrared spectrometer (FT-IR), and 721 cm derived from polyethylene. ^-1 The peak of was observed. Furthermore, as a result of analyzing with a thermogravimetry apparatus (TGA), the amount of inorganic components in the obtained layered silicate / polymer composite composition (I) was 46% by weight.
[0086]
3. Composite of polyethylene resin and layered silicate
Weight of polyethylene resin (trade name “HB530”, manufactured by Nippon Polychem Co., Ltd.) and layered silicate / polymer composite composition (I) in a small extruder (trade name “TEX30”, manufactured by Nippon Steel Works) The mixture was fed at a ratio of 92.3 / 7.7, melt-kneaded at a set temperature of 200 ° C., and the extruded strand was pelletized with a pelletizer. The obtained pellets were molded into a plate having a thickness of 3 mm or a thickness of 100 μm by a hot press adjusted to 200 ° C. to prepare a sample for evaluation.
[0087]
(Example 2)
1. Synthesis of organic layered silicates containing transition metal complexes and alkylammonium salts
Montmorillonite (trade name “Bengel A”, manufactured by Toyshun Mining Co., Ltd.) 5 g and distilled water 495 g were put into a 1 L beaker, and xylene (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was added to further expand the interlayer distance. The mixture was stirred for about 2 hours at room temperature using a motor stirrer to prepare a swelling slurry of montmorillonite. Next, 0.27 g of dicyclopentadienyl titanium dichloride was added to the swelling slurry, and the mixture was stirred at room temperature for 24 hours using a motor stirrer. Further, 2.88 g of distearyldimethylammonium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.001 g of concentrated hydrochloric acid as cationic surfactants were added to the swelling slurry, and the mixture was stirred at room temperature for 8 hours using a motor stirrer. After that, the solid content was separated with a centrifugal separator. In order to remove the unnecessary component adhering to the solid content, the operation of separating the solid content with a centrifugal separator was further repeated twice after the solid content was dispersed again in distilled water. The obtained solid content was vacuum-dried at 50 ° C. for 48 hours using a vacuum dryer, and the resulting composition was used as an organic layered silicate containing a transition metal complex / alkylammonium salt. The yield was 8.01g. This was designated as MMT-B.
[0088]
2. Polymerization of ethylene
After replacing the 300 mL pressure-resistant glass container with argon, MMT-B, which is the transition metal complex / alkylammonium salt-containing organic layered silicate (dicyclopentadienyl titanium dichloride / distearyldimethylammonium chloride added montmorillonite) prepared earlier, 7.00 g was added and dissolved in 150 mL of toluene. Further, 30 mL of methylalumoxane (10 wt% toluene solution, manufactured by Aldrich) was added dropwise from a syringe over 10 minutes. Next, ethylene gas is introduced into the container, and the inside of the system is 1.1 kg / cm. ² The polymerization was carried out at 0 ° C. for 4 hours. After the reaction, 300 mL of methanol was added to the system to stop the reaction, and the precipitated polymer was recovered to obtain 17.5 g of a layered silicate / polymer composite composition (II).
[0089]
The obtained layered silicate / polymer composite composition (II) was analyzed using a Fourier transform infrared spectrometer (FT-IR), and 721 cm derived from polyethylene. ^-1 The peak of was observed. Furthermore, as a result of analyzing with a thermogravimetry apparatus (TGA), the amount of inorganic components in the obtained layered silicate / polymer composite composition (II) was 43% by weight.
[0090]
3. Composite of polyethylene resin and layered silicate
Weight of polyethylene resin (trade name “HB530”, manufactured by Nippon Polychem Co., Ltd.) and layered silicate / polymer composite composition (II) in a small extruder (trade name “TEX30”, manufactured by Nippon Steel Works) The mixture was fed at a ratio of 92.3 / 7.7, melt-kneaded at a set temperature of 200 ° C., and the extruded strand was pelletized with a pelletizer. The obtained pellets were molded into a plate having a thickness of 3 mm or a thickness of 100 μm by a hot press adjusted to 200 ° C. to prepare a sample for evaluation.
[0091]
(Example 3)
While stirring 500 g of distearyldimethyl quaternary ammonium salt-treated montmorillonite (trade name “New Sven D”, manufactured by Toyoshun Mining Co., Ltd.) in a Henschel mixer, 2 of vinyltrimethoxysilane (reagent, manufactured by Shin-Etsu Chemical Co., Ltd.) 100 g of a weight% aqueous solution was added dropwise over 3 minutes. After completion of the dropwise addition, the mixture was further stirred for 10 minutes. The obtained treated powder was held in a vacuum dryer adjusted to 70 ° C. and dried for 8 hours. The obtained powder was designated as MMT-C.
[0092]
In a small extruder (trade name “TEX30”, manufactured by Nippon Steel Co., Ltd.), polypropylene resin (trade name “EA9”, manufactured by Nippon Polychem Co., Ltd.) and MMT-C were 92.3 / 7.7 by weight. 2,5-dimethyl-2,5-bis (t as a peroxide for the purpose of graft-reacting the unsaturated bond contained in vinyltrimethoxysilane to the polypropylene resin. -Butylperoxy) hexane (trade name “Perhexa 25B”, half-life temperature of 1 minute: 180 ° C., manufactured by NOF Corporation) was used. The peroxide was added using a plunger pump so that it might become 0.1 weight% with respect to polypropylene resin. The mixture was melt-kneaded at a set temperature of 200 ° C., and the extruded strand was pelletized with a pelletizer. The obtained pellets were molded into a plate having a thickness of 3 mm or a thickness of 100 μm by a hot press adjusted to 200 ° C. to prepare a sample for evaluation.
[0093]
(Example 4)
As the layered silicate, montmorillonite (trade name “Bengel A”, manufactured by Toyoshun Mining Co., Ltd.) previously ion-exchanged with distearyldimethyl quaternary ammonium salt was used. This was designated as MMT-D. As the polypropylene resin, 15 parts of maleic anhydride-modified propylene oligomer (product) with respect to 100 parts of polypropylene resin (trade name “EA9”, manufactured by Nippon Polychem Co., Ltd.) in order to increase the affinity between the polypropylene resin and the layered silicate. The name “Yumex 1001”, functional group content: 0.23 mmol / g, manufactured by Sanyo Chemical Industries, Ltd.) was used.
The above-mentioned polypropylene resin and layered silicate were fed into a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) and melt-kneaded at a preset temperature of 200 ° C. The composition was polypropylene resin / maleic anhydride modified polypropylene oligomer / MMT-D = 82.3 / 10 / 7.7 (weight ratio).
[0094]
The obtained composite composition was preheated at 200 ° C. for 5 minutes by a melt press and then pressed at a pressure of 9.8 MPa for 1 minute to form a 1 mm thick sheet. A 1 mm thick sheet was cut into a 3 cm square, placed in an autoclave, the autoclave was sealed, and the internal temperature was set to a temperature 10 ° C. higher than the melting point of the polypropylene resin. Next, carbon dioxide gas was injected into the autoclave at a high pressure, and the inner pressure in the autoclave was maintained at 16.7 MPa for 30 minutes. Furthermore, the temperature in the autoclave was set to a temperature 10 ° C. lower than the melting point of the polypropylene resin. In this state, the gas in the autoclave was exhausted at once, and the internal pressure was returned to normal pressure. The obtained foam was molded into a plate-like material having a thickness of 3 mm or a thickness of 100 μm by a hot press adjusted to 200 ° C. to prepare a sample for evaluation.
[0095]
(Example 5)
In a small extruder (trade name “TEX30”, manufactured by Nippon Steel Co., Ltd.), 84.6 parts of polypropylene resin (trade name “EA9”, manufactured by Nippon Polychem), maleic anhydride-modified propylene oligomer (trade name “YUMEX 1001”) ”, Functional group content: 0.23 mmol / g, manufactured by Sanyo Chemical Industries, Ltd.) 5 parts, and 7.7 parts of MMT-D were fed, melt-kneaded at a set temperature of 200 ° C., and the extruded strand was pelletized. And pelletized. The obtained pellets were molded into a plate-like product having a thickness of 3 mm or a thickness of 100 μm by a hot press adjusted to 200 ° C. to prepare a sample for evaluation.
[0096]
(Example 6)
In the same manner as in Example 5 except that 5 parts of ammonium polyphosphate (trade name “AP422”, manufactured by Nippon Polyolefin Co., Ltd.) was added to a small extruder (trade name “TEX30”, manufactured by Nippon Steel Works). An evaluation sample was produced.
[0097]
(Example 7)
A sample for evaluation was produced in the same manner as in Example 6 except that 5 parts of phenylphosphonic acid (manufactured by Daihachi Chemical Co., Ltd.) was added instead of 5 parts of ammonium polyphosphate.
[0098]
(Example 8)
A sample for evaluation was prepared in the same manner as in Example 6 except that 25 parts of higher fatty acid-treated magnesium hydroxide (trade name “Kisuma 5J”, manufactured by Kyowa Chemical Industry Co., Ltd.) was added instead of 5 parts of ammonium polyphosphate. did.
[0099]
Example 9
An evaluation sample was produced in the same manner as in Example 6 except that 20 parts of melamine cyanurate (Nissan Chemical Co., Ltd.) was added instead of 5 parts of ammonium polyphosphate.
[0100]
(Example 10)
For evaluation in the same manner as in Example 6 except that 5 parts of talc (trade name “P-6”, average particle size: 3.7 μm, manufactured by Nippon Talc Co., Ltd.) was added instead of 5 parts of ammonium polyphosphate. A sample was made.
[0101]
(Example 11)
Instead of 5 parts of ammonium polyphosphate, a block copolymer consisting of a polypropylene block and a carboxylic acid-modified polypropylene block (trade name “CB-OM12”, molecular weight of segment (A) block and segment (B) block: all 1 .5x10 ⁴ (Manufactured by Kuraray Co., Ltd.) An evaluation sample was prepared in the same manner as in Example 6 except that 5 parts of maleic anhydride-modified propylene oligomer was not added.
[0102]
(Example 12)
Instead of polypropylene resin and maleic anhydride modified propylene oligomer, ethylene-ethyl acrylate copolymer (trade name “A4250”, manufactured by Nippon Polyolefin Co., Ltd.) and maleic anhydride modified ethylene oligomer (trade name “ER403A”, Nippon Polyolefin, respectively) A sample for evaluation was produced in the same manner as in Example 5 except that the product manufactured by the company was used.
[0103]
(Example 13)
A sample for evaluation was prepared in the same manner as in Example 12 except that maleic anhydride-modified ethylene oligomer (trade name “ER403A”, manufactured by Nippon Polyolefin Co., Ltd.) was not used.
[0104]
(Example 14)
Instead of polypropylene resin and maleic anhydride modified propylene oligomer, ethylene-ethyl acrylate copolymer (trade name “A4250”, manufactured by Nippon Polyolefin Co., Ltd.) and maleic anhydride modified ethylene oligomer (trade name “ER403A”, Nippon Polyolefin, respectively) A sample for evaluation was produced in the same manner as in Example 8 except that the product manufactured by Kogyo Co., Ltd. was used.
[0105]
(Example 15)
Furthermore, a sample for evaluation was prepared in the same manner as in Example 14 except that 1.5 parts of copper (II) oxide (manufactured by Nisshin Chemco) was added.
[0106]
(Example 16)
A sample for evaluation was prepared in the same manner as in Example 15 except that 1.0 part of tin oxide (II) (manufactured by Showa Chemical Industry Co., Ltd.) was added instead of 1.5 parts of copper (II) oxide.
[0107]
(Example 17)
A sample for evaluation was produced in the same manner as in Example 15 except that 1.0 part of zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd.) was added instead of 1.5 parts of copper oxide (II).
[0108]
(Example 18)
Furthermore, a sample for evaluation was produced in the same manner as in Example 14 except that 2.0 parts of p-phenylphenol was added.
[0109]
(Example 19)
In a small extruder (trade name “TEX30”, manufactured by Nippon Steel Works), 87.3 parts of polyethylene resin (trade name “HB530”, manufactured by Nippon Polychem) and 7.7 parts of MMT-D were fed and set. The mixture was melt-kneaded at a temperature of 200 ° C., and the extruded strand was pelletized with a pelletizer. The obtained pellets were molded into a plate-like product having a thickness of 3 mm or a thickness of 100 μm by a hot press adjusted to 200 ° C. to prepare a sample for evaluation.
[0110]
(Example 20)
Further, an evaluation sample was prepared in the same manner as in Example 19 except that 5 parts of ammonium polyphosphate (trade name “AP422”, manufactured by Nippon Polyolefin Co., Ltd.) was added.
[0111]
(Example 21)
For evaluation in the same manner as in Example 20, except that the amount of polyethylene resin (trade name “HB530”, manufactured by Nippon Polychem Co., Ltd.) was 85.3 parts, and 2 parts of trihydroxyethyl isocyanurate (THEIC) was further added. A sample was made.
[0112]
(Example 22)
5 g of montmorillonite (trade name “Bengel A”, manufactured by Toyoshun Mining Co., Ltd.) and 495 g of distilled water were placed in a beaker and stirred for about 2 hours at room temperature using a motor stirrer to prepare a swelling slurry of montmorillonite. Next, 0.27 g of dodecyltriphenylphosphonium bromide was added to the swollen slurry, and the mixture was stirred for 24 hours at room temperature using a motor stirrer, and then the solid content was separated using a centrifugal separator. In order to remove the unnecessary component adhering to the solid content, the operation of separating the solid content with a centrifugal separator was further repeated twice after the solid content was dispersed again in distilled water. The obtained solid content was vacuum-dried at 50 ° C. for 48 hours using a vacuum dryer, and the composition obtained was used as a phosphonium salt-containing layered silicate. Yield was 5.10 g. This was designated as MMT-E. When the MMT-E was analyzed with a thermogravimetric apparatus (TGA), the amount of inorganic components in the MMT-E was 46% by weight.
[0113]
In a small extruder (trade name “TEX30”, manufactured by Nippon Steel Co., Ltd.), 82.3 parts of polypropylene resin (trade name “EA9”, manufactured by Nippon Polychem Co., Ltd.), maleic anhydride-modified propylene oligomer (trade name “YUMEX 1001”) ”, Functional group content: 0.23 mmol / g, Sanyo Chemical Industries, Ltd.) 7.7 parts and MMT-E 7.7 parts are fed, melt kneaded at a set temperature of 200 ° C., and the extruded strand is pelletized. And pelletized. The obtained pellets were molded into a plate-like product having a thickness of 3 mm or a thickness of 100 μm by a hot press adjusted to 200 ° C. to prepare a sample for evaluation.
[0114]
(Example 23)
Further, an evaluation sample was prepared in the same manner as in Example 22 except that 5 parts of ammonium polyphosphate (trade name “AP422”, manufactured by Nippon Polyolefin Co., Ltd.) was added.
[0115]
(Example 24)
Further, an evaluation sample was prepared in the same manner as in Example 22 except that 20 parts of higher fatty acid-treated magnesium hydroxide (trade name “Kisuma 5J”, manufactured by Kyowa Chemical Industry Co., Ltd.) was added.
[0116]
(Example 25)
Further, a sample for evaluation was produced in the same manner as in Example 22 except that 20 parts of silane coupling agent-treated magnesium hydroxide (trade name “Kisuma 5PH”, manufactured by Kyowa Chemical Industry Co., Ltd.) was added.
[0117]
(Example 26)
Furthermore, a sample for evaluation was prepared in the same manner as in Example 22 except that 20 parts of melamine cyanurate (manufactured by Nissan Chemical Co., Ltd.) was added.
[0118]
(Example 27)
Instead of the maleic anhydride-modified propylene oligomer, a block copolymer comprising a polypropylene block and a carboxylic acid-modified polypropylene block (trade name “CB-OM12”, segment (A) block and molecular weight of segment (B) block: all 1.5 × 10 ⁴ The sample for evaluation was produced like Example 22 except having used Kuraray Co., Ltd.).
[0119]
(Example 28)
Instead of polypropylene resin and maleic anhydride-modified propylene oligomer, polyethylene resin (trade name “HB530”, manufactured by Nippon Polychem) and maleic anhydride-modified ethylene oligomer (trade name “ER403A”, manufactured by Nippon Polyolefin) were used, respectively. A sample for evaluation was produced in the same manner as in Example 22 except that.
[0120]
(Example 29)
Further, an evaluation sample was produced in the same manner as in Example 28 except that 5 parts of ammonium polyphosphate (trade name “AP422”, manufactured by Nippon Polyolefin Co., Ltd.) was added.
[0121]
(Example 30)
Further, an evaluation sample was prepared in the same manner as in Example 28 except that 20 parts of higher fatty acid-treated magnesium hydroxide (trade name “Kisuma 5J”, manufactured by Kyowa Chemical Industry Co., Ltd.) was added.
[0122]
(Example 31)
Further, a sample for evaluation was produced in the same manner as in Example 28 except that 20 parts of silane coupling agent-treated magnesium hydroxide (trade name “Kisuma 5PH”, manufactured by Kyowa Chemical Industry Co., Ltd.) was added.
[0123]
(Example 32)
Further, an evaluation sample was prepared in the same manner as in Example 28 except that 20 parts of melamine cyanurate (Nissan Chemical Co., Ltd.) was added.
[0124]
(Example 33)
Furthermore, it carried out similarly to Example 28 except having added 20 parts of magnesium hydroxide (brand name "Kisuma 5J", Kyowa Chemical Industry Co., Ltd.) and 1.5 parts of copper (II) oxide (made by Nisshin Kecom Co., Ltd.). A sample for evaluation was prepared.
[0125]
(Example 34)
Instead of the maleic anhydride-modified ethylene oligomer, a block copolymer consisting of a polyethylene block and a carboxylic acid-modified polyethylene block (trade name “CB-OM22”, manufactured by Kuraray Co., Ltd.) was added in the same manner as in Example 28. Thus, a sample for evaluation was produced.
[0126]
(Example 35)
5 g of montmorillonite (trade name “Bengel A”, manufactured by Toyoshun Mining Co., Ltd.) and 495 g of distilled water were placed in a beaker and stirred for about 2 hours at room temperature using a motor stirrer to prepare a swelling slurry of montmorillonite. Next, 0.7 g of nickel chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the swelling slurry and stirred for 4 hours at room temperature using a motor stirrer, and then 0.7 g of distearyldimethyl quaternary ammonium salt was added. After adding and stirring for 24 hours, the solid content was separated by a centrifugal separator. In order to remove the unnecessary component adhering to the solid content, the operation of separating the solid content with a centrifugal separator was further repeated twice after the solid content was dispersed again in distilled water. A composition obtained by vacuum drying the obtained solid content at 50 ° C. for 48 hours using a vacuum dryer was used as a nickel ion exchange layered silicate. Yield was 5.10 g. This was designated as MMT-F. When the MMT-F was analyzed with a thermogravimetric apparatus (TGA), the amount of inorganic components in the MMT-F was 80% by weight.
[0127]
In a small extruder (trade name “TEX30”, manufactured by Nippon Steel Co., Ltd.), 82.3 parts of polypropylene resin (trade name “EA9”, manufactured by Nippon Polychem), maleic anhydride-modified propylene oligomer (trade name “YUMEX 1001”) ”, Functional group content: 0.23 mmol / g, manufactured by Sanyo Chemical Industries, Ltd.) 7.7 parts, ammonium polyphosphate (trade name“ AP422 ”, manufactured by Nippon Polyolefin Co., Ltd.), and 7.7 parts of MMT-F. The mixture was fed and melt-kneaded at a set temperature of 200 ° C., and the extruded strand was pelletized with a pelletizer. The obtained pellets were molded into a plate-like product having a thickness of 3 mm or a thickness of 100 μm by a hot press adjusted to 200 ° C. to prepare a sample for evaluation.
[0128]
(Example 36)
Instead of polypropylene resin and maleic anhydride-modified propylene oligomer, polyethylene resin (trade name “HB530”, manufactured by Nippon Polychem) and maleic anhydride-modified ethylene oligomer (trade name “ER403A”, manufactured by Nippon Polyolefin) were used, respectively. A sample for evaluation was produced in the same manner as in Example 35 except that.
[0129]
(Comparative Example 1)
A sample for evaluation was prepared in the same manner as in Example 1 except that a polypropylene resin (trade name “EA9”, manufactured by Nippon Polychem Co., Ltd.) was used alone without adding the layered silicate.
[0130]
(Comparative Example 2)
Except that 100 parts of polypropylene resin (trade name “EA9”, manufactured by Nippon Polychem Co., Ltd.) and 100 parts of ammonium polyphosphate (trade name “AP422”, manufactured by Nippon Polyolefin Co., Ltd.) were added without adding layered silicate. In the same manner as in Example 1, a sample for evaluation was produced.
[0131]
(Comparative Example 3)
Example 1 was performed except that 100 parts of aluminum hydroxide (metal hydroxide) was added to 100 parts of polypropylene resin (trade name “EA9”, manufactured by Nippon Polychem) without adding layered silicate. A sample for evaluation was prepared.
[0132]
(Comparative Example 4)
Except for adding 7.7 parts of purified montmorillonite (trade name “Kunipia F”, manufactured by Kunimine Kogyo Co., Ltd.) not subjected to ion exchange to 92.3 parts of polypropylene resin (trade name “EA9”, manufactured by Nippon Polychem Co., Ltd.) A sample for evaluation was produced in the same manner as in Example 1.
[0133]
(Comparative Example 5)
Add 7.7 parts of distearyl dimethyl quaternary ammonium salt-treated montmorillonite (trade name “New Sven D”, manufactured by Toyshun Mining Co., Ltd.) to 92.3 parts of polypropylene resin (trade name “EA9”, manufactured by Nippon Polychem Co., Ltd.) A sample for evaluation was produced in the same manner as in Example 1 except that.
[0134]
(Comparative Example 6)
An evaluation sample was prepared in the same manner as in Comparative Example 3 except that a polyethylene resin (trade name “HB530”, manufactured by Nippon Polychem Co., Ltd.) was used instead of the polypropylene resin.
[0135]
(Comparative Example 7)
A sample for evaluation was produced in the same manner as in Comparative Example 3 except that an ethylene-ethyl acrylate copolymer (trade name “A4250”, manufactured by Nippon Polyolefin Co., Ltd.) was used instead of the polypropylene resin.
[0136]
Performance of the samples for evaluation obtained in Examples 1 to 36 and Comparative Examples 1 to 7 ((1) average interlayer distance, (2) elongation, (3) combustion residue state and yield point Stress, (4) maximum heat generation rate, and (5) self-extinguishing property) were evaluated by the following methods. The results are shown in Tables 1 and 2.
[0137]
(1) Average interlayer distance: 2θ of a diffraction peak obtained from diffraction of a layered silicate layer in an evaluation sample is measured using an X-ray diffractometer (trade name “RINT1100”, manufactured by Rigaku Corporation). Then, the (001) plane spacing of the layered silicate was calculated by the following formula “black diffraction formula”.
λ = 2 d sin θ (λ = 1.54 d: plane spacing of layered silicate, θ: diffraction angle)
D obtained from the above formula was defined as the average interlayer distance.
[0138]
(2) Elongation: At the time of rupture of a dumbbell-shaped No. 3 specimen as an evaluation sample in an atmosphere of a temperature of 20 ° C. and a humidity of 50% RH in accordance with JIS K 6251 “Tensile test method for vulcanized rubber” The elongation was measured to 750%. When it did not break to 750%, it was described as 750% or more, and when it broke at less than 750%, the elongation at break was described.
[0139]
(3) State of combustion residue and yield point stress: In accordance with ASTM E 1354 “Combustion test method for building materials”, a test piece (100 mm × 100 mm × 3 mm thickness) of an evaluation sample is applied with a cone calorimeter at 50 kW / m ² It was burned by irradiating the heat rays. Next, the state of the combustion residue was visually observed, and the yield point stress when the combustion residue was compressed at 0.1 cm / s was measured using a strength measuring device.
[Criteria]
○ …… Yield point stress 4.9 × 10 ³ Pa or higher
(◎ ... Yield point stress 1.5 × 10 ⁴ Pa or higher)
[0140]
(4) Maximum heat generation rate: 50 kW / m of a sample specimen (100 mm × 100 mm × 3 mm thickness) for evaluation as in (3) with a cone calorimeter ² Is irradiated with a heat ray of ² ) Was measured.
[Criteria]
○… Maximum heat generation rate 800 kW / m ² Less than
×… Maximum heat generation rate 800 kW / m ² Super
[0141]
(5) Self-extinguishing property: In accordance with ASTM D 2863 “Standard test method for plastic flammability by oxygen index”, a test piece (70 mm × 6 mm × 3 mm thickness) of an evaluation sample is made self-supporting, and a combustion test is performed. Self-extinguishing properties were evaluated according to the following criteria. In this test, the numerical value of the minimum oxygen concentration (volume%) in the mixed gas of oxygen and nitrogen necessary for the test piece to maintain combustion is called the oxygen index, and combustion is performed at a predetermined oxygen concentration. The combustion was maintained when the combustion continued for 3 minutes or more, or the combustion continued for 50 mm or more within 3 minutes, and the oxygen concentration at that time was defined as the oxygen index of the test piece. That is, self-extinguishing is meant at oxygen concentrations below the oxygen index.
[0142]
[Table 1]

[0143]
[Table 2]

[0144]
* About Examples 5, 8, 9, 12, 14-19, 24, 25, 30, 31, and 33, self-extinguishing property was able to be confirmed.
As is apparent from Tables 1 and 2, all of the samples for evaluation comprising the polyolefin resin compositions of Examples 1 to 36 of the present invention have a sintered body formed of layered silicate during combustion, and combustion The shape of the residue is maintained, the combustion residue has a yield point when compressed at 0.1 cm / s, and the yield point stress is 4.9 × 10 ³ Pa or higher. As a result, shape collapse did not occur even after combustion, excellent self-extinguishing properties, and excellent flame retardancy without fire spread. Also, the elongation at break was 750% or more, and the flexibility was excellent.
[0145]
On the other hand, as is apparent from Table 2, Comparative Example 1 to Comparative Example 3 that did not contain the layered silicate, and the evaluation sample comprising the polyolefin resin compositions of Comparative Example 6 and Comparative Example 7, Since the combustion residue was not generated or the shape of the combustion residue was not maintained, the self-extinguishing property was poor and the flame retardancy was inferior. Moreover, the sample for evaluation which consists of the polyolefin-type resin composition of the comparative example 4 whose average interlayer distance of layered silicate was less than 3 nm was inferior in the self-extinguishing property and inferior in flame retardance.
[0146]
In Comparative Example 5, although the interlayer distance was 3.5 nm, it was considered that there was no layered silicate dispersed in 5 layers or less, and the flame retardancy was not greatly affected. Even in the formation of the combustion film, the formation was limited to local formation, and the strength could not be maintained.
[0147]
【The invention's effect】
Since this invention consists of an above-mentioned structure, the sintered compact by a layered silicate is formed at the time of combustion, and the shape of a combustion residue is hold | maintained. As a result, shape collapse does not occur even after combustion, excellent shape retention and self-extinguishing properties, no fire spread, excellent flame retardancy, excellent mechanical strength, and transparency are also maintained. A polyolefin resin composition can be provided. Further, according to the present invention, the physical properties of the polyolefin resin such as the elastic modulus and gas barrier properties can be remarkably improved, the heat resistance based on the increase of the heat distortion temperature due to the molecular chain restraint, and the nucleating agent effect due to the inorganic crystals. Various physical properties such as dimensional stability based on the above can be greatly improved.

Claims (18)

A polyolefin resin composition comprising 100 parts by weight of a polyolefin resin, 0.1 to 100 parts by weight of a layered silicate, and 20 to 60 parts by weight of a metal hydroxide ,
Yield point stress is 4.9 × 10 ³ Pa or more when a combustion residue obtained by heating and burning for 30 minutes under a heating condition of 50 kW / m ² is compressed at 0.1 cm / s. A polyolefin resin composition. The polyolefin resin composition according to claim 1, wherein the maximum heat generation rate when heated and burned for 30 minutes under a heating condition of 50 kW / m ² is 800 kW / m ² or less.   Polyolefin resins include ethylene homopolymers, propylene homopolymers, copolymers of ethylene or propylene and α-olefins copolymerizable therewith, copolymers of ethylene and (meth) acrylic esters, 3. The polyolefin resin composition according to claim 1, wherein the polyolefin resin composition is at least one resin selected from the group consisting of a copolymer of ethylene and vinyl acetate.   4. The polyolefin resin composition according to claim 1, 2 or 3, wherein the layered silicate is montmorillonite and / or swellable mica.   The polyolefin resin composition according to claim 1, 2, 3, or 4, wherein the layered silicate contains a metal ion as an exchangeable cation in the crystal structure.    6. The polyolefin resin composition according to claim 5, wherein a part or all of the metal ions are exchanged with a cationic surfactant.   The cationic surfactant is a homopolymer of a (meth) acrylic monomer having a quaternary ammonium salt structure, or a (meth) acrylic monomer having a quaternary ammonium salt structure and other (meth) acrylic monomers and 7. The polyolefin resin composition according to claim 6, which is a copolymer with a styrene monomer.   The polyolefin-based resin composition according to claim 6, wherein the cationic surfactant is a quaternary alkylphosphonium salt having an alkyl group having 6 or more carbon atoms.   The layered silicate has an average interlaminar distance of (001) plane measured by wide angle X-ray diffraction measurement method of 3 nm or more and includes those dispersed in a polyolefin resin composition in a state of 5 layers or less. The polyolefin resin composition according to claim 1, 2, 3, 4, 5, 6, 7 or 8.   The layered silicate has an average interlayer distance of (001) plane measured by wide-angle X-ray diffractometry is 6 nm or more, 2, 2, 3, 4, 5, 6, 7, 8 or 9. The polyolefin resin composition according to 9. The polyolefin resin composition according to claim 1 or 2, further comprising 0.5 to 100 parts by weight of at least one compound selected from the group consisting of a phosphorus compound and a melamine derivative . The phosphorus compound is at least one phosphorus compound selected from the group consisting of red phosphorus, ammonium polyphosphate, and a phosphorus compound represented by the following general formula (1). Polyolefin resin composition.
R ³ (R ² ) (OR ¹ ) P═O (1)
In the formula, 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, an alkoxyl group, or an aryl group. Or an aryloxy group is shown, and R ¹ , R ² and R ³ may be the same or different.   Furthermore, 0.5-20 weight part of silicate compounds other than layered silicate are contained, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 characterized by the above-mentioned. The polyolefin-based resin composition described.   Furthermore, 0.1-10 weight part of metal oxides are contained, The polyolefin of Claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13 characterized by the above-mentioned. -Based resin composition. Furthermore, it contains an AB type block copolymer composed of a segment (A) block having a functional group reactive to layered silicate and a segment (B) block having affinity for polyolefin resin. The polyolefin resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.   Furthermore, 0.01-30 weight part of compounds which have an aromatic hydroxyl group are contained, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, The polyolefin resin composition according to 13, 14 or 15.   Claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16 for coating an electric wire or sheath A thermoplastic resin characterized by being used as an application.   An insulated wire comprising the thermoplastic resin according to claim 17.