JP2012126870A - Flame-retardant, heat-resistant, low dielectric-constant, and low dielectric-loss-tangent polyolefin resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer material which is an environmentally compatible material, has high heat resistance, and includes a flame retarder that imparts flame retardancy without impairing the characteristics of low dielectric constant and low dielectric loss tangent and is free of problems from the viewpoint of environmental problems or the like.SOLUTION: The polymer material is a polyolefin resin composition which is obtained by blending a polyolefin (A), obtained by (co)polymerizing at least one kind of olefin selected from 5-20C α-olefins, with a bis(polybromophenyl)alkane being a bromine-based flame retarder (B) free of environmental pollution problems.

Description

  TECHNICAL FIELD The present invention relates to a flame retardant, heat resistant, low dielectric constant / low dielectric loss tangent polyolefin resin composition having heat resistance and imparting flame retardancy while maintaining the characteristics of low dielectric loss and low dielectric loss tangent. .

  In recent years, the signal band of information communication devices such as mobile phones and the CPU clock time of computers have reached the GHz band, and higher frequencies have been advanced.

  The dielectric loss of an electrical signal is proportional to the product of the square root of the dielectric constant of the insulator forming the circuit, the dielectric loss tangent and the frequency of the signal used. Therefore, the higher the frequency of the signal used, the greater the dielectric loss.

  Dielectric loss attenuates an electrical signal and impairs the reliability of the signal. Therefore, in order to suppress this, it is necessary to select a material having a small dielectric constant and dielectric loss tangent for the insulator.

As such materials, polymer materials such as fluororesins, curable polyolefins, cyanate ester resins, curable polyphenylene oxide, allyl-modified polyphenylene ether, polyetherimide modified with divinylbenzene or divinylnaphthalene have been proposed. (Patent Document 1)
In addition, electronic devices such as computers have a portion that can be a source of ignition because a high voltage is applied or the temperature is high. Because of this, there is a possibility of developing into a fire. For example, high flame resistance and heat resistance are also required for insulating substrate materials used in computers and the like.

Here, in order to impart flame retardancy to the polymer material, conventionally, flame retardants such as halogen flame retardants, red phosphorus, phosphate esters, nitrogen-containing compounds, metal hydroxides, metal oxides, etc. have been added. Has been studied. (Patent Document 2, Patent Document 3)
Among these, halogen-based flame retardants, among them, halogenated hydrocarbon compounds, particularly decabromodiphenyl ether have been used as preferable compounds. However, in recent years, decabromodiphenyl ether has been subject to regulation in the RoHS directive, and its use is restricted. (Non-Patent Document 1)
Furthermore, when the flame retardant is added to the polymer material, problems such as a decrease in dielectric properties such as dielectric constant and dielectric loss tangent may occur, and studies using various flame retardants have been made. (Patent Document 4, Non-Patent Document 2)
On the other hand, polymer materials used for electronic devices such as computers have recently been required to be materials that do not burden the environment due to waste plastic disposal problems. It is desired.

Japanese Patent Laid-Open No. 2002-249531 JP 2001-288309 A JP 2000-351906 A JP 2003-34211 A

Environmental Project No. 1142 2007 Fujikura Technical Review No. 109 51-54 Oct 2005

  In view of the above-described background art, the problem to be solved by the present invention is an environment-adaptive material, that is, a polymer material that is easy to recycle and has high heat resistance, and has a low dielectric constant and a low dielectric loss tangent. An object of the present invention is to provide a polymer material containing a flame retardant capable of imparting flame retardancy without impairing characteristics and having no problem from the viewpoint of environmental problems.

  Specifically, it is suppressed by the prior art by blending a flame retardant having a specific structure with a polyolefin having a specific structure having a low dielectric constant and a low dielectric loss tangent and also having high heat resistance. To provide a flame-retardant, heat-resistant, low dielectric constant / low dielectric loss tangent polyolefin resin composition having greatly improved flame retardancy without lowering dielectric properties such as dielectric constant and dielectric loss tangent, which have been difficult to achieve It is in.

  As a result of investigations by the present inventors in order to solve the above problems, a polyolefin resin composition in which bis (polybromophenyl) alkane having no environmental pollution problem is blended with a polyolefin having a specific structure can solve the above problems. As a result, the present invention has been completed.

  That is, the flame retardancy, heat resistance, low dielectric constant / low dielectric loss tangent polyolefin resin composition according to the present invention has the following characteristics.

  Bromine represented by the following general formula (I) with respect to 100 parts by weight of polyolefin (A) obtained by (co) polymerizing at least one olefin selected from α-olefins having 5 to 20 carbon atoms It comprises 30-80 parts by weight of flame retardant (B).

(In general formula (I), n represents an integer of 1 to 5, p represents an integer of 1 to 5, and q represents an integer of 1 to 5)
The polyolefin resin composition may further include 5 to 40 parts by weight of a flame retardant aid (C).

  The polyolefin resin composition may further include 1 to 10 parts by weight of an anti-drip agent (D).

  The polyolefin (A) is preferably a polyolefin obtained by (co) polymerizing at least one olefin selected from branched α-olefins having 5 to 20 carbon atoms, and 4-methyl-1- More preferably, it is a pentene polymer.

  In the brominated flame retardant (B), in general formula (I), n is preferably 1, p is 5, and q is 5.

  The flame retardant aid (C) is preferably antimony trioxide.

  Furthermore, the anti-drip agent (D) is preferably polytetrafluoroethylene.

  Since the polyolefin resin composition of the present invention has a polyolefin resin as a constituent element, the polyolefin resin composition is excellent in recyclability. Further, since the polyolefin resin has a specific polymer structure, it also has heat resistance.

  Further, in the present invention, by using a flame retardant having a specific structure, it is possible to impart high flame retardancy without impairing the characteristics of the low dielectric constant and low dielectric loss tangent inherent in the polyolefin resin.

  The polyolefin resin composition having such characteristics is suitably used for insulating substrate materials for electronic devices such as computers, electric wire coating materials, connectors, and other electrical components that require flame resistance, heat resistance, and low dielectric properties. It is done.

Hereinafter, each component which comprises the polyolefin resin composition concerning this invention is explained in full detail.
[Polyolefin (A)]
The polyolefin (A) of the present invention is obtained by (co) polymerizing at least one olefin selected from α-olefins having 5 to 20 carbon atoms. Here, (co) polymerization is a concept including the case where the α-olefin described above is polymerized alone or the case where other olefins are copolymerized together with the α-olefin described above.

  Specific examples of at least one olefin selected from α-olefins having 5 to 20 carbon atoms include 1-pentene, 3-methyl-1-butene, 2-methyl-1-butene, 1-hexene, 4- Methyl-1-pentene, 3-methyl-1-pentene, 2-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. Is mentioned. Among these, from the viewpoint of the heat resistance and low dielectric properties of the resulting polyolefin, the olefin used is preferably a branched α-olefin, such as 3-methyl-1-butene and 4-methyl-1-pentene. More preferred is 4-methyl-1-pentene.

  When the polyolefin (A) is a copolymer, examples of other olefins copolymerized with an α-olefin having 5 to 20 carbon atoms include ethylene and α-olefins having 3 to 20 carbon atoms (the above-mentioned number of carbon atoms). Except for α-olefins selected from 5 to 20 α-olefins). Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene and 3-methyl- 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like are included, and among these, α-C 5 -C 20 is preferable. An olefin, more preferably an α-olefin having 8 to 20 carbon atoms. These olefins can be used alone or in combination of two or more.

  When the polyolefin (A) is a copolymer, the content of units derived from at least one olefin selected from α-olefins having 5 to 20 carbon atoms constituting the copolymer is 95 mol% or more, preferably It is 98 mol% or more.

  The polyolefin (A) of the present invention preferably satisfies the following requirements (Ai) and (A-ii).

  (Ai) The melt flow rate (MFR) is 1 to 500 g / 10 min, preferably 2 to 100 g / 10 min, more preferably 3 to 30 g / 10 min. MFR is measured under the conditions of a measurement temperature of 260 ° C. and a load of 5 kgf according to ASTM D1238. When the MFR is in the above range, the fluidity of the obtained polyolefin resin composition in the molding die is increased.

  (A-ii) Melting | fusing point (Tm) is 220-250 degreeC, Preferably it is 224-245 degreeC, More preferably, it is 228-240 degreeC. When the melting point is less than 220 ° C., the strength of the polyolefin (A) itself is lowered, and thus the strength of the resulting polyolefin resin composition may not be sufficient. When the melting point exceeds 250 ° C., the impact strength and toughness of the resulting polyolefin resin composition may be lowered. The melting point of the polyolefin (A) can be measured in a nitrogen atmosphere in a temperature range of 30 to 280 ° C. in accordance with JIS-K7121. At this time, the heating rate and the cooling rate may each be 10 ° C./min.

  Polyolefin (A) contains at least one olefin selected from α-olefins having 5 to 20 carbon atoms in the presence of a known olefin polymerization catalyst such as a Ziegler-Natta catalyst, a metallocene catalyst or a so-called postmetallocene catalyst. Manufactured by (co) polymerization.

  More specifically, the polyolefin (A) is produced by polymerizing the olefin constituting the polyolefin (A) in the presence of a polymerization catalyst containing a transition metal catalyst component and a cocatalyst component.

  The polymerization reaction of the olefin in the production of the polyolefin (A) can be performed by a liquid phase polymerization method such as solution polymerization, suspension polymerization, bulk polymerization method, gas phase polymerization method, and other known polymerization methods. Preferably, the polyolefin (A) is produced by a liquid phase polymerization method such as solution polymerization and suspension polymerization (slurry polymerization), more preferably a suspension polymerization (slurry polymerization) method.

  When the polymerization is performed by a liquid phase polymerization method, an inert hydrocarbon can be used as a solvent, and an olefin that is liquid under reaction conditions can also be used. The polymerization can be carried out in any of batch, semi-continuous and continuous methods; the polymerization can be carried out in two or more stages by changing reaction conditions. By supplying hydrogen to the polymerization reaction system, the molecular weight of the obtained polymer can be adjusted, and the melt flow rate of the polyolefin (A) can be adjusted.

  The polymerization temperature and polymerization pressure in the polymerization differ depending on the polymerization method and the type of olefin to be polymerized. Usually, the polymerization temperature is set to 10 to 200 ° C., preferably 30 to 150 ° C., and the polymerization pressure is set to normal pressure to 5 MPaG, preferably 0.05 to 4 MPaG.

  The transition metal catalyst component used for the production of the polyolefin (A) is a solid titanium catalyst or metallocene catalyst having magnesium and titanium as transition metals and halogen and an electron donor as ligands; preferably solid It is a titanium catalyst.

  The transition metal catalyst component is particularly preferably a magnesium compound suspended in an inert hydrocarbon solvent, a compound having two or more ether bonds with a plurality of atoms in between as an electron donor, and a liquid titanium compound Is a solid titanium catalyst obtained by contacting the catalyst. The solid titanium catalyst has a titanium atom, a magnesium atom, a halogen, and a plurality of ether bonds.

  Examples of the inert hydrocarbon solvent used for the production of the solid titanium catalyst include hexane, decane, and dodecane; examples of the magnesium compound include anhydrous magnesium chloride and methoxymagnesium chloride; Examples of the compound having two or more ether bonds with a plurality of atoms in between include 2-isobutyl-2-isopropyl-1,3-dimethoxypropane and 2-isopentyl-2-isopropyl-1,3-dimethoxypropane. It is done.

  By selecting the type of electron donor contained in the solid titanium catalyst, the stereoregularity of the resulting polymer can be adjusted. Thereby, the melting point of the polymer can be adjusted.

  The atomic ratio of halogen and titanium (halogen / titanium) in the solid titanium catalyst is usually 2 to 100, preferably 4 to 90. In the solid titanium catalyst, the molar ratio of the compound containing two or more ether bonds to titanium (compound containing two or more ether bonds / titanium) is 0.01 to 100, preferably 0.2 to 10. The atomic ratio of magnesium and titanium (magnesium / titanium) in the solid titanium catalyst is 2 to 100, preferably 4 to 50.

  Furthermore, suitable examples of the polymerization catalyst used in the olefin polymerization for obtaining the polyolefin (A) include JP-A-57-63310, JP-A-58-83006, JP-A-3-706, Magnesium-supported titanium catalysts described in JP-A-3476793, JP-A-4-218508, JP-A-2003-105022, etc .; WO01 / 53369, WO01 / 27124, Metallocene catalysts described in, for example, Kaihei 3-19396 or JP-A-02-41303 are included. The use of a magnesium-supported titanium catalyst containing a polyether as an electron donor component is particularly preferable because a polyolefin (A) having a relatively narrow molecular weight distribution tends to be obtained.

  When the monomer polymerization in the production of the polyolefin (A) is performed by a liquid phase polymerization method, the solid titanium catalyst is converted to titanium atoms per liter of the total liquid volume of 0.0001 to 0.5 mmol, preferably It is preferably used in an amount of 0.0005 to 0.1 mmol.

  The transition metal catalyst component is preferably suspended in an inert organic solvent (preferably a saturated aliphatic hydrocarbon) and supplied to the polymerization reaction system.

  The transition metal catalyst component is preferably used as a solid catalyst component preliminarily polymerized with an α-olefin to be subjected to polymerization. By prepolymerization, 0.1 to 1000 g, preferably 0.3 to 500 g, more preferably 1 to 200 g of α-olefin is polymerized per 1 g of the transition metal catalyst component. The prepolymerization can be performed at a catalyst concentration higher than the catalyst concentration in the reaction system in the polymerization of olefins.

The cocatalyst component used for the production of the polyolefin (A) is preferably an organometallic compound catalyst component, and specifically includes an organoaluminum compound. Organic aluminum compounds, for ^example, represented by _R a _{n AlX 3-n.}

R ^{a in} R ^a _n AlX _3-n is ^a hydrocarbon group having 1 to 12 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, and an aryl group. Specific examples include a methyl group, ethyl group, n-propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group. X in R ^a _n AlX _3-n is halogen or hydrogen, and n is 1 to 3.

Specific examples of the organoaluminum compound represented by R ^a _n AlX _3-n include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; isoprenyl Alkenyl aluminum such as aluminum; Dialkylaluminum halide such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide; Methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride And Alkyl aluminum sesquihalides such as ethyl aluminum sesquibromide; Alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide; Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride It is.

  Of these, alkylaluminums such as triethylaluminum and triisobutylaluminum are preferred.

When the transition metal catalyst component is a solid titanium catalyst, the amount of the cocatalyst component (organometallic compound catalyst component) used in the production of the polyolefin (A) is 0.1 to 1 × per 1 g of the solid titanium catalyst. The amount may be such that 10 ⁶ g, preferably 1 × 10 ² to 1 × 10 ⁶ g of polymer is formed. The amount of the cocatalyst component (organometallic compound catalyst component) used is 0.1 to 1000 mol, preferably about 0.5 to 500 mol, more preferably 1 per mol of titanium atom in the solid titanium catalyst. ~ 200 moles.

Since the polyolefin (A) is a thermoplastic resin, a product produced using the polyolefin resin composition according to the present invention can be easily recycled after use, and can be referred to as an environment-adaptive material.
[Brominated flame retardant (B)]
The brominated flame retardant (B) used in the present invention is 1,2-bis (polybromophenyl) alkane represented by the following general formula (I).

  In general formula (I), n shows the integer of 1-5. In the polyolefin resin composition of the present invention, in order not to impair the characteristics of the low dielectric constant and low dielectric loss tangent inherent in the polyolefin (A), the polarity of the flame retardant compound represented by the general formula (I) Is small, that is, it is required to have good symmetry in terms of molecular structure. From such a viewpoint, in the general formula (I), n is preferably an integer of 1 to 3, and more preferably 1.

  In general formula (I), p shows the integer of 1-5, q shows the integer of 1-5. The flame retardant compound has a tendency to increase the effect of flame retardancy as the bromine content increases. Therefore, both p and q preferably represent integers of 3 to 5, more preferably 5 (all bromine atoms in the benzene ring). Is a mode of bonding). In addition, when p and q are 1-4, the bonding position of the bromine atom to the benzene ring is not particularly limited, and there is no difference in the flame retardancy effect at any location.

  The brominated flame retardant (B) represented by the general formula (I) is not particularly limited as long as it satisfies the ranges of n, p, and q. However, the bromine content is high and the molecular structure is symmetric. 1,2-bis (pentabromophenyl) ethane is particularly preferable.

  The addition amount of the brominated flame retardant (B) is preferably 30 to 80 parts by weight with respect to 100 parts by weight of the polyolefin (A). By adding in this range, sufficient flame retardancy is added to the polyolefin (A ). In addition, when there is little addition amount of a brominated flame retardant (B) from the said range, sufficient flame retardant effect may not be acquired, and the added amount of a brominated flame retardant (B) is more than the said range. In many cases, the flame retardant effect is enhanced, but the dielectric properties and heat resistance of the polyolefin resin composition are lowered, the specific gravity of the resulting polyolefin resin composition is increased, and further, kneading is stable. In some cases, it may become difficult.

It should be noted that decabromodiphenyl ether, which has been used particularly well as an existing flame retardant compound mentioned in the background section, has a dioxin-like structure and, as impurities, highly accumulating hexabromodiphenyl ether, heptabromo Since diphenyl ether, octabromodiphenyl ether, and nonabromodiphenyl ether are contained, there is a concern of adversely affecting the environment. On the other hand, the brominated flame retardant (B) represented by the general formula (I) used in the present invention is not structurally harmful to the environment, and does not contain the above impurities. It is particularly preferable in that it can be used as a compound having a small influence.
[Flame Retardant (C)]
Examples of the flame retardant aid (C) that can be used in the present invention include antimony compounds. By using an antimony compound as the flame retardant aid (C), the amount of the brominated flame retardant (B) used can be reduced, and the deterioration of dielectric properties can be further suppressed.

  Examples of such antimony compounds include antimony trioxide, antimony tetraoxide, antimony pentoxide, and sodium antimonate, and among these, antimony trioxide is particularly preferable.

  When using a flame-retardant adjuvant (C), it is preferable that the addition amount shall be 5-40 weight part with respect to 100 weight part of polyolefin (A). In addition, from the said range, when there are few addition amounts of a flame retardant adjuvant (C), sufficient flame-retardant effect may not be acquired, and the addition amount of a flame retardant adjuvant (C) from the said range. In many cases, problems such as a decrease in dielectric properties of the polyolefin resin composition may occur.

When the flame retardant aid (C) is used, the ratio of the flame retardant aid (C) to the brominated flame retardant (B) (flame retardant aid (C) / brominated flame retardant (B)) is 0. .15 to 0.65 is preferable, and good flame retardancy can be obtained by adjusting the amount of the brominated flame retardant (B) and the flame retardant auxiliary (C) so as to be within this range. it can.
[Anti-drip agent (D)]
Examples of the anti-drip agent (D) that can be used in the present invention include substances that can increase the melt viscosity when added to the polyolefin (A). As such a substance, a fluororesin is mentioned as a suitable example, and polytetrafluoroethylene is particularly preferable among them.

  Since a fluorine-based resin such as polytetrafluoroethylene has a property of forming a fiber when force is applied to the particles, the polyolefin resin composition to which the anti-drip agent (D) having such characteristics is added is burned. In some cases, the molten resin can be prevented from dripping and the spread of the polyolefin resin composition can be prevented.

  Thus, by adding the anti-drip agent (D) to the polyolefin resin composition, fragmentation of the resin melted by combustion is suppressed, and the effect that fire spread can be prevented is exhibited. Therefore, when the anti-drip agent (D) is included, even if the addition amount of the brominated flame retardant (B) is reduced, the same flame retardancy (non-flame spread) as when the brominated flame retardant (B) is used alone. Thus, it is possible to prevent a decrease in dielectric properties of the polyolefin resin composition.

When using an anti-drip agent (D), it is preferable that the addition amount shall be 1-10 weight part with respect to 100 weight part of polyolefin (A). In addition, from the said range, when there are few addition amounts of an anti-drip agent (D), sufficient anti-drip effect may not be acquired and by extension, sufficient flame-retardant effect may not be acquired. . When the addition amount of the anti-drip agent (D) is larger than the above range, there may be a problem in moldability and physical properties of the polyolefin resin composition.
[Other resins]
An elastomer resin may be further added to the polyolefin resin composition according to the present invention. By adding the resin, impact resistance and toughness can be imparted to the polyolefin resin composition.

  Examples of elastomer resins that can be used in the present invention include propylene / α-olefin block copolymers, ethylene / α-olefin random copolymers, ethylene / α-olefin / non-conjugated polyene random copolymers, hydrogenated propylene / Examples include α-olefin block copolymers, other elastic polymers, and mixtures thereof.

  Examples of the α-olefin include those similar to the α-olefin having 3 to 20 carbon atoms described as the copolymer component of the polyolefin (A) (when propylene is included as a component of the elastomer resin, carbon Propylene is excluded from α-olefins having 3 to 20 atoms). These α-olefins may be used alone or in combination of two or more.

  As examples of the non-conjugated polyene, a compound having two or more non-conjugated unsaturated bonds can be used without limitation, and examples thereof include non-conjugated cyclic polyene and non-conjugated chain polyene. A combination of the above may also be used.

When the elastomer resin is added, the addition amount is 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polyolefin (A). .
[Other additives]
If necessary, other additive components may be added to the polyolefin resin composition according to the present invention. Examples of other additive components include heat stabilizers, weather stabilizers, light stabilizers, antistatic agents, fillers, lubricants, slip materials, antiblocking agents, hydrochloric acid absorbents, dispersants, crystal nucleating agents, Softeners, antifogging agents, dyes, pigments, natural oils, synthetic oils, waxes, flame retardants and the like are included. For example, known phenol stabilizers, organic phosphite stabilizers, thioether stabilizers, hindered amine stabilizers, higher fatty acid metal salts such as calcium stearate, inorganic oxides and the like.

When adding another additive component, it is preferable that the addition amount is 0.01-10 weight part with respect to 100 weight part of polyolefin (A).
[Production method of polyolefin resin composition]
The polyolefin resin composition according to the present invention includes, for example, a polyolefin (A), a brominated flame retardant (B), and other optional components (a flame retardant aid (C), an anti-drip agent (D), etc.). After mixing at the above-mentioned addition ratio, it is obtained by melt-kneading.

The method of melt kneading is not particularly limited, and can be performed using a melt kneading apparatus such as a commercially available extruder.
[Molded body]
The polyolefin resin composition concerning this invention is processed into a molded object according to the use used.

  The processing means for the molded body is not particularly limited, and the polyolefin resin composition pellets obtained by melt kneading or impregnation are conventionally known in various ways, specifically, for example, injection molding, profile extrusion molding, and the like. , Pipe forming method, tube forming method, dissimilar molded body covering forming method, injection blow forming method, direct blow forming method, T-die sheet or film forming method, inflation film forming method, press forming method, etc. It can be formed into a tray shape, a sheet shape, a rod shape, a film shape, or a coating of various molded bodies.

  The molded article of the polyolefin resin composition of the present invention exhibits good heat resistance, flame retardancy, and dielectric properties. Therefore, it is used after being processed into wire covering materials and electronic parts (capacitors, ink cartridges, home appliance housings, ECU cases, switches, inverter parts), structural members (TV housings) and the like that require flame resistance and dielectric properties. it can.

  EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.

The materials used in Examples and Comparative Examples are as follows.
(1) Polyolefin (A)
The following polyolefins (commercially available) were used.

Poly-4-methyl-1-pentene (trade name: TPX, brand name: RT18 (melting point: 232 ° C. MFR (ASTM D1238, 260 ° C., 5 kgf): 27 g / 10 min), manufactured by Mitsui Chemicals, Inc.)
(2) Brominated flame retardant (B)
The following brominated flame retardants (all of which are commercially available) were used.

1) 1,2-bis (pentabromophenyl) ethane (SAYTEX 8010, made by Albemarle Japan)
2) Decabromodiphenyl ether (Nonen DP10-F, manufactured by Maruhishi Oil Industries)
3) 1,2-bis (tetrabromophthalimide) ethane (SAYTEX BT-93, manufactured by Albemarle Japan)
4) Brominated polystyrene I (SAYTEX HP-3010, Albemarle Japan)
5) Brominated polystyrene II (SAYTEX HP-7010, Albemarle Japan)
(3) Flame retardant aid (C)
The following flame retardant aids (commercially available) were used.

Antimony trioxide (PATOX-M, manufactured by Nippon concentrate)
(4) Anti-drip agent (D)
The following anti-drip agent (commercially available) was used.

  Polytetrafluoroethylene (TLP10F, Mitsui / DuPont Chloro Chemical)

Test conditions in the examples and comparative examples are as follows.
(1) MFR
Based on ASTM D1238, the measurement was performed at 260 ° C. under a load of 5 kgf.
(2) Injection molding conditions for producing each test piece of polyolefin resin composition Injection molding machine: M-70B (φ = 32 mm)
Injection temperature: 270 to 300 ° C., mold temperature: 40 to 60 ° C., cooling time: 15 to 20 seconds Test piece type: square plate, UL test piece (3) relative permittivity, dielectric loss tangent By cylindrical cavity resonator method , Measured at 12 GHz and room temperature.
(4) UL94V Combustion Test Measured using a sample having a thickness of 1/32 inch in accordance with ASTM D 3801.

[Example 1]
100 parts by weight of polyolefin (A) and 42.9 parts by weight of 1,2-bis (pentabromophenyl) ethane as a brominated flame retardant (B) were added to a twin-screw extruder (manufacturer name: Ikekai Co., Ltd., model number PCM45). , Φ = 43 mm, L / D = 30, flame retardant: top feed input, use of nitrogen gas purge, cylinder temperature: 280 ° C.) to obtain a resin composition 1. Each test piece was obtained from the obtained resin composition 1 under the above-described injection molding conditions. Table 1 summarizes the MFR of the resin composition 1, the results of measuring the relative dielectric constant and dielectric loss tangent of the test piece, and the UL94V combustion test results.

[Example 2]
100 parts by weight of polyolefin (A), 46.2 parts by weight of 1,2-bis (pentabromophenyl) ethane as a brominated flame retardant (B), 7.7 parts by weight of antimony trioxide as a flame retardant aid (C), A twin screw extruder (manufacturer name: Ikegai, model number PCM45, φ = 43 mm, L / D = 30, flame retardant / flame retardant: top feed input, nitrogen gas purge used, cylinder temperature: 280 ° C.) The resin composition 2 was obtained by kneading. Each test piece was obtained from the obtained resin composition 2 under the above-described injection molding conditions. Table 1 summarizes the results of measuring the MFR of the resin composition 2, the relative permittivity of the test piece, the dielectric loss tangent, and the UL94V combustion test results.

[Example 3]
100 parts by weight of polyolefin (A), 61.0 parts by weight of 1,2-bis (pentabromophenyl) ethane as brominated flame retardant (B), and 8.5 parts by weight of antimony trioxide as flame retardant aid (C) A resin composition 3 was obtained in the same manner as in Example 2 except that. Table 1 summarizes the results of measuring the MFR of the resin composition 3, the relative permittivity of the test piece, the dielectric loss tangent, and the UL94V combustion test results.

[Example 4]
100 parts by weight of polyolefin (A), 39.3 parts by weight of 1,2-bis (pentabromophenyl) ethane as brominated flame retardant (B), 24.6 parts by weight of antimony trioxide as flame retardant aid (C), A resin composition 4 was obtained in the same manner as in Example 2 except that. Table 1 summarizes the results of measuring the MFR of the resin composition 4, the relative permittivity of the test piece, the dielectric loss tangent, and the UL94V combustion test results.

[Example 5]
100 parts by weight of polyolefin (A), 54.5 parts by weight of 1,2-bis (pentabromophenyl) ethane as the brominated flame retardant (B), 27.3 parts by weight of antimony trioxide as the flame retardant aid (C), A resin composition 5 was obtained in the same manner as in Example 2 except that. Table 1 summarizes the results of measuring the MFR of the resin composition 5, the relative permittivity of the test piece, the dielectric loss tangent, and the UL94V combustion test results.

[Example 6]
100 parts by weight of polyolefin (A), 73.5 parts by weight of 1,2-bis (pentabromophenyl) ethane as brominated flame retardant (B), 30.6 parts by weight of antimony trioxide as flame retardant aid (C), A resin composition 6 was obtained in the same manner as in Example 2 except that. Table 1 summarizes the results of measuring the MFR of the resin composition 6, the relative permittivity of the test piece, the dielectric loss tangent, and the UL94V combustion test results.

[Example 7]
100 parts by weight of polyolefin (A), 46.9 parts by weight of 1,2-bis (pentabromophenyl) ethane as brominated flame retardant (B), 7.8 parts by weight of antimony trioxide as flame retardant aid (C), 1.6 parts by weight of polytetrafluoroethylene as anti-drip agent (D), twin screw extruder (manufacturer name: Ikegai, model number PCM45, φ = 43 mm, L / D = 30, flame retardant / flame retardant) Auxiliary agent: top feed input, anti-drip agent: top feed, nitrogen gas purge used, cylinder temperature: 280 ° C.) were kneaded to obtain resin composition 7. Each test piece was obtained from the obtained resin composition 2 under the above-described injection molding conditions. Table 1 summarizes the results of measuring the MFR of the resin composition 7, the relative permittivity of the test piece, the dielectric loss tangent, and the UL94V combustion test results.

[Example 8]
100 parts by weight of polyolefin (A), 48.4 parts by weight of 1,2-bis (pentabromophenyl) ethane as brominated flame retardant (B), 8.1 parts by weight of antimony trioxide as flame retardant aid (C), A resin composition 8 was obtained in the same manner as in Example 7 except that 4.8 parts by weight of polytetrafluoroethylene was used as the anti-drip agent (D). Table 1 summarizes the results of measuring the MFR of the resin composition 8, the relative permittivity of the test piece, the dielectric loss tangent, and the UL94V combustion test results.

[Example 9]
100 parts by weight of polyolefin (A), 50.0 parts by weight of 1,2-bis (pentabromophenyl) ethane as brominated flame retardant (B), 8.3 parts by weight of antimony trioxide as flame retardant aid (C), A resin composition 9 was obtained in the same manner as in Example 7 except that 8.3 parts by weight of polytetrafluoroethylene was used as the anti-drip agent (D). Table 1 summarizes the MFR of the resin composition 9, the results of measuring the relative dielectric constant and dielectric loss tangent of the test piece, and the UL94V combustion test results.

[Comparative Example 1]
Each test piece was obtained from only 100 parts by weight of the polyolefin (A) under the above-described injection molding conditions. Table 2 summarizes the results of measuring the MFR, the relative dielectric constant of the test piece, the dielectric loss tangent, and the UL94V combustion test result of the resin composition 7.

[Comparative Example 2]
Resin composition 10 was prepared in the same manner as in Example 1 except that 100 parts by weight of polyolefin (A) and 25.0 parts by weight of 1,2-bis (pentabromophenyl) ethane as brominated flame retardant (B) were used. Obtained. Table 2 summarizes the results of measuring the MFR, the relative dielectric constant of the test piece, the dielectric loss tangent, and the UL94V combustion test result of the resin composition 10.

[Comparative Example 3]
Example 2 except that 100 parts by weight of polyolefin (A), 50.0 parts by weight of decabromodiphenyl ether as brominated flame retardant (B), and 16.7 parts by weight of antimony trioxide as flame retardant aid (C) were used. Thus, a resin composition 11 was obtained. Table 2 summarizes the MFR of the resin composition 11, the results of measuring the relative dielectric constant and dielectric loss tangent of the test piece, and the UL94V combustion test results.

[Comparative Example 4]
100 parts by weight of polyolefin (A), 63.8 parts by weight of 1,2-bis (tetrabromophthalimide) ethane as brominated flame retardant (B), and 8.6 parts by weight of antimony trioxide as flame retardant aid (C) A resin composition 12 was obtained in the same manner as in Example 2 except that. Table 2 summarizes the MFR of the resin composition 12, the relative dielectric constant of the test piece, the measurement result of the dielectric loss tangent, and the UL94V combustion test result.

[Comparative Example 5]
Example 2 with the exception of 100 parts by weight of polyolefin (A), 61.0 parts by weight of brominated polystyrene I as brominated flame retardant (B), and 8.5 parts by weight of antimony trioxide as flame retardant aid (C) A resin composition 13 was obtained by the same method. Table 2 summarizes the results of measuring the MFR, the relative permittivity of the test piece, the dielectric loss tangent, and the UL94V combustion test result of the resin composition 13.

[Comparative Example 6]
Example 2 with the exception of 100 parts by weight of polyolefin (A), 61.0 parts by weight of brominated polystyrene II as brominated flame retardant (B), and 8.5 parts by weight of antimony trioxide as flame retardant aid (C) The resin composition 14 was obtained by the same method. Table 2 summarizes the results of measuring the MFR of the resin composition 14, the relative permittivity of the test piece, the dielectric loss tangent, and the UL94V combustion test results.

  In Examples 1 to 9, as a result of the UL94V combustion test, V-0 equivalent was achieved with a 1/32 inch test piece.

  Examples 1-9 showed a low dielectric loss tangent compared with the comparative example 1 which used polyolefin (A) independently.

  On the other hand, Comparative Example 2 was able to realize a dielectric loss tangent lower than that of Comparative Example 1, but the result of the combustion test was V-2 equivalent and inferior to Examples 1-9.

  From these results, the resin composition according to the present invention includes a certain amount of 1,2-bis (pentabromophenyl) ethane as the brominated flame retardant (B), thereby achieving both flame retardancy and low dielectric loss tangent. It was confirmed that a functional resin composition can be realized.

  Moreover, when decabromodiphenyl ether was used as the brominated flame retardant (B) as in Comparative Example 3, the relative permittivity deteriorated most among Examples 1 to 9 and Comparative Examples 1 to 6. This is considered to be derived from the polarity of the ether bond. Decabromodiphenyl ether has a problem of environmental pollution and is a substance that tends to be refrained from use.

  As in Comparative Examples 4 to 6, when a brominated flame retardant (B) other than 1,2-bis (pentabromophenyl) ethane was used, the dielectric loss tangent was deteriorated as compared with Comparative Example 1. It was.

  Examples 1-9 showed high MFR compared with the comparative example 1 which used polyolefin (A) independently. This is thought to be due to the plasticizing effect of the flame retardant.

  The polyolefin resin composition of the present invention exhibits good flame retardancy and dielectric properties. Therefore, it can be applied to wire covering materials and electronic parts (capacitors, ink cartridges, home appliance housings, ECU cases, switches, inverter parts), structural members (TV housings) and the like that require flame retardancy and dielectric properties.

Claims (8)

Bromine represented by the following general formula (I) with respect to 100 parts by weight of polyolefin (A) obtained by (co) polymerizing at least one olefin selected from α-olefins having 5 to 20 carbon atoms A polyolefin resin composition comprising 30 to 80 parts by weight of a flame retardant (B).

(In general formula (I), n represents an integer of 1 to 5, p represents an integer of 1 to 5, and q represents an integer of 1 to 5)   The polyolefin resin composition according to claim 1, further comprising 5 to 40 parts by weight of a flame retardant aid (C).   The polyolefin resin composition according to claim 1 or 2, further comprising 1 to 10 parts by weight of an anti-drip agent (D).   4. The polyolefin according to claim 1, wherein the polyolefin (A) is a polyolefin obtained by (co) polymerizing at least one olefin selected from branched α-olefins having 5 to 20 carbon atoms. The polyolefin resin composition described in 1.   The polyolefin resin composition according to any one of claims 1 to 3, wherein the polyolefin (A) is a 4-methyl-1-pentene polymer.   In the said general formula (I), n is 1, p is 5, and q is 5, The polyolefin resin composition of any one of Claims 1-5.   The polyolefin resin composition according to any one of claims 2 to 6, wherein the flame retardant aid (C) is antimony trioxide.   The polyolefin resin composition according to any one of claims 3 to 7, wherein the anti-drip agent (D) is polytetrafluoroethylene.