Copolymer composition and its uses

Abstract

To provide a molded article having high tensile elongation and a high tanδ, while having fire resistance given by a copolymer composition containing a 4-methyl-1-pentene based copolymer and a specific fire retardant.SOLUTION: A copolymer composition (X) of the invention contains a 4-methyl-1-pentene based copolymer (A) satisfying a specific requirement of 50-95 pts.mass and a fire retardant (B) of 5-50 pts.mass [The sum of (A) and (B) is 100 pts.mass.] and satisfies the following requirements of (X-a) and (X-b). The requirement (X-a): The tanδ peak temperature is in the range of 0-45°C, which is obtained by dynamic viscoelasticity measurement in the temperature range of -70 to 180°C at 10 rad / s (1.6 Hz) frequency. The requirement (X-b): The tanδ peak value is 0.5 or more, which is obtained by dynamic viscoelasticity measurement in the temperature range of -70 to 180°C at 10 rad / s (1.6 Hz) frequency.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a 4-methyl-1-pentene copolymer composition containing a flame retardant, and to pellets, molded articles, films and heat radiating members made from said composition. More specifically, the present invention relates to a molded article having high tensile elongation and high tan δ while being flame retardant, which is made from a copolymer composition containing a specific 4-methyl-1-pentene copolymer and a specific flame retardant. [Background technology]

[0002] Compared to polyethylene and polypropylene, 4-methyl-1-pentene copolymers have superior heat resistance, transparency, electrical properties, etc., and are widely used in a variety of applications, particularly known as industrial release films and capacitor films (Patent Document 1).In addition, an industrial film has been disclosed that exhibits stress relaxation properties by adjusting the molecular weight and composition of a 4-methyl-1-pentene copolymer to lower its melting point, making it possible to hold foreign matter in an enclosed state (Patent Document 2).

[0003] Meanwhile, attempts have been made to use materials obtained by mixing 4-methyl-1-pentene copolymers with additives. By using such materials, strength, weight, thermal conductivity, electrical properties, and the like that could not be achieved with conventional thermoplastic resins alone can be obtained. For example, Patent Document 3 describes a resin composition that achieves both flame retardancy and low dielectric properties by adding a flame retardant to a 4-methyl-1-pentene copolymer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-11182 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-169685 [Patent Document 3] Japanese Patent Application Laid-Open No. 2012-237019 Summary of the Invention [Problem to be solved by the invention]

[0005] 4-methyl-1-pentene copolymers have excellent stress relaxation properties, high tensile elongation, and high tan δ, but because they are general olefin resins, they lack flame retardancy, which limits their use. The material described in the aforementioned Patent Document 3 achieves both flame retardancy and low dielectric properties by adding a flame retardant to the 4-methyl-1-pentene copolymer, but has the problem of being unable to maintain high tensile elongation and high tan δ.

[0006] Therefore, the problem to be solved by the present invention is to provide a molded article having high tensile elongation and high tan δ while having flame retardancy due to a copolymer composition containing a 4-methyl-1-pentene copolymer and a specific flame retardant. [Means for solving the problem]

[0007] In view of the above circumstances, the present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that the above-mentioned problems can be solved by using a composition containing a 4-methyl-1-pentene copolymer (A) and a specific flame retardant (B), thereby completing the present invention.

[0008] That is, the present invention relates to the following [1] to [7]. [1] A copolymer composition (X) comprising 50 to 95 parts by mass of a 4-methyl-1-pentene copolymer (A) satisfying at least one of the following requirements (Aa) and (Ab), and 5 to 50 parts by mass of a flame retardant (B) (the total of (A) and (B) being 100 parts by mass), and satisfying the following requirements (Xa) and (Xb); Requirement (Aa) The copolymer is composed of 60 to 97 mol% of structural units (i) derived from 4-methyl-1-pentene and 3 to 40 mol% of structural units (ii) derived from an α-olefin having 2 to 4 carbon atoms (the total of structural units (i) derived from 4-methyl-1-pentene and structural units (ii) derived from an α-olefin having 2 to 4 carbon atoms being 100 mol%); Requirement (Ab) The melting point measured by differential scanning calorimetry (DSC) is 160°C or less, or no melting point is observed; Requirement (Xa) - The tan δ peak temperature obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in the temperature range of 70 to 180°C is in the range of 0 to 45°C; Requirement (Xb) The tan δ peak value obtained by performing dynamic viscoelasticity measurement in a temperature range of −70 to 180° C. at a frequency of 10 rad / s (1.6 Hz) is 0.5 or more. [2] The copolymer composition (X) according to item [1], wherein the flame retardant (B) has a phosphate group. [3] The copolymer composition (X) according to item [2], wherein the flame retardant (B) has two or more phosphate groups. [4] A pellet comprising the copolymer composition (X) according to any one of items [1] to [3]. [5] A molded article comprising the copolymer composition (X) according to any one of items [1] to [3]. [6] A film or sheet comprising the copolymer composition (X) according to any one of items [1] to [3]. [7] A heat radiation member comprising the copolymer composition (X) according to any one of items [1] to [3]. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a copolymer composition and a molded article to which flame retardancy has been imparted while maintaining the high tensile elongation and high tan δ that are characteristic of 4-methyl-1-pentene copolymers. DETAILED DESCRIPTION OF THE INVENTION

[0010] Specific embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments and can be practiced with appropriate modifications within the scope of the object of the present invention. In this specification, the term "polymer" is used to include homopolymers and copolymers unless otherwise specified.

[0011] The copolymer composition (X) of the present invention and the molded article made of said composition contain a 4-methyl-1-pentene copolymer (A) and a flame retardant (B), each of which will be explained below.

[0012] <4-methyl-1-pentene copolymer (A)> The 4-methyl-1-pentene copolymer (A) (hereinafter sometimes abbreviated as "copolymer (A)"), which is one of the components of the copolymer composition (X) of the present invention, is a polymer that satisfies at least one of the following requirements (Aa) and (Ab):

[0013] <Requirement (Aa)> It is composed of 60 to 97 mol % of structural units derived from 4-methyl-1-pentene (hereinafter, sometimes referred to as "structural units (i)"). ) and 3 to 40 mol % of structural units derived from at least one α-olefin having 2 to 4 carbon atoms (hereinafter, sometimes referred to as "structural units (ii)"). ) (the total of structural units (i) and structural units (ii) is taken as 100 mol %).

[0014] Requirement (Aa) specifies that the 4-methyl-1-pentene copolymer (A) contains a specific ratio of structural units (i) derived from 4-methyl-1-pentene and structural units (ii) derived from an α-olefin having 2 to 4 carbon atoms (excluding 4-methyl-1-pentene).

[0015] In the 4-methyl-1-pentene copolymer (A) according to the present invention, the lower limit of the amount of structural unit (i) is 60 mol%. The amount of structural unit (i) is preferably 65 mol%, more preferably 68 mol%. Meanwhile, the upper limit of the amount of structural unit (ii) is 97 mol%. The amount of structural unit (ii) is preferably 93 mol%, more preferably 87 mol%.

[0016] In the 4-methyl-1-pentene copolymer (A) of the present invention, if the amount of the structural unit (i) derived from 4-methyl-1-pentene is equal to or greater than the above lower limit, the tan δ peak temperature measured by dynamic viscoelasticity will be near room temperature, making it easy to adjust the tan δ peak temperature of the resulting copolymer composition within the range described below. On the other hand, if the amount of the structural unit (i) derived from 4-methyl-1-pentene is equal to or less than the above upper limit, the copolymer will have relaxivity at room temperature.

[0017] In the 4-methyl-1-pentene copolymer (A) according to the present invention, the upper limit of the amount of the structural unit (ii) is 40 mol%, preferably 35 mol%, and more preferably 32 mol%, while the lower limit of the amount of the structural unit (ii) is 3 mol%, preferably 7 mol%, and more preferably 13 mol%.

[0018] The content (mol %) of each structural unit constituting the 4-methyl-1-pentene copolymer (A) according to the present invention is: 13 The measurement is carried out by C-NMR. Details of the measurement method are as described in the Examples below.

[0019] The structural unit (ii) constituting the 4-methyl-1-pentene copolymer (A) according to the present invention may be derived from one compound or from two or more compounds. Specific examples of the structural unit (ii) include ethylene, propylene, and 1-butene, and among these α-olefins, propylene is preferred.

[0020] By selecting propylene as the structural unit (ii), the tan δ peak temperature of the 4-methyl-1-pentene copolymer (A) can be easily adjusted to the above range, the tan δ peak temperature of the resulting copolymer composition can be set to the following range, and a molded article that imparts high stress relaxation properties can be easily obtained.

[0021] <Requirements (Ab)> The melting point measured by differential scanning calorimetry (DSC) is less than 160°C, or no melting point is observed.

[0022] The 4-methyl-1-pentene copolymer (A) according to the present invention preferably has a melting point of less than 160°C or no melting point as measured by differential scanning calorimetry (DSC), a melting point of 150°C or less or no melting point as measured, and more preferably has a melting point of 140°C or less or no melting point as measured.

[0023] The 4-methyl-1-pentene copolymer (A) according to the present invention preferably has a melting point of 110°C or higher or no melting point, more preferably no melting point, as measured by differential scanning calorimetry (DSC).

[0024] A copolymer composition containing a 4-methyl-1-pentene copolymer (A) that satisfies requirement (Ab) has high stress relaxation properties. The 4-methyl-1-pentene copolymer (A) according to the present invention preferably satisfies at least one of the following requirements (Ac) to (Ae) in addition to the requirements (Aa) and (Ab).

[0025] <Requirements (Ac)> The tan δ peak temperature determined by dynamic viscoelasticity measurement in a temperature range of -70 to 180°C at a frequency of 10 rad / s (1.6 Hz) is preferably in the range of 0 to 45°C, more preferably 15 to 45°C, and even more preferably 25 to 45°C. A copolymer composition containing a 4-methyl-1-pentene copolymer (A) having a tan δ peak temperature within the above range can exhibit better stress relaxation properties around room temperature.

[0026] <Requirements (Ad)> The tan δ peak value, obtained by dynamic viscoelasticity measurement at a temperature range of -70 to 180°C and a frequency of 10 rad / s (1.6 Hz), is 0.5 or more, preferably 0.8 or more, and more preferably 1.0 or more. A tan δ peak value of 0.5 or more has an excellent ability to dissipate energy when stress is applied, and the resulting molded article has improved stress relaxation and stress absorption. The higher the tan δ peak value, the greater the above-mentioned effects, so there is no particular upper limit, but the range obtained by normal measurement is 5.0 or less.

[0027] <Requirements (Ae)> The density is preferably 830 to 870 kg / m 3 , more preferably 830 to 860 kg / m 3 , and more preferably 830 to 850 kg / m 3 is.

[0028] Details of the density measurement method are as described in the Examples below. The density of the 4-methyl-1-pentene copolymer (A) according to the present invention can be appropriately changed by changing the amount of the structural unit (i) in the 4-methyl-1-pentene copolymer. A 4-methyl-1-pentene copolymer (A) having a density within the above range is advantageous because it has good flexibility and mechanical properties.

[0029] The 4-methyl-1-pentene copolymer (A) according to the present invention more preferably satisfies one or more, even more preferably two or more, and particularly preferably all of the following requirements (Af) to (Ah).

[0030] <Requirements (Af)> The intrinsic viscosity [η] measured in decalin at 135° C. is preferably in the range of 0.1 to 5.0 dl / g, more preferably 0.5 to 4.0 dl / g, and even more preferably 1.0 to 3.5 dl / g.

[0031] As will be described later, the intrinsic viscosity [η] of the 4-methyl-1-pentene copolymer (A) can be adjusted to the above-mentioned range by controlling the molecular weight by using hydrogen during the polymerization of the copolymer (A), and can freely obtain low molecular weight to high molecular weight copolymers. The details of the measurement method are as described in the examples below.

[0032] The intrinsic viscosity [η] of copolymer (A) is Approximately 20 mg of polymer was dissolved in 25 ml of decalin, and the specific viscosity η was measured using an Ubbelohde viscometer in an oil bath at 135°C. sp After adding 5 ml of decalin to this decalin solution to dilute it, measure the specific viscosity η sp Repeat this dilution procedure two more times and measure η when the concentration (C) is extrapolated to 0. sp The value of / C is calculated as the intrinsic viscosity [η] (unit: dl / g) using the following formula 1. [η]=lim(η sp / C) (C→0)...Formula 1

[0033] <Requirements (Ag)> The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is preferably 500 to 10,000,000, more preferably 1,000 to 5,000,000, and even more preferably 1,000 to 2,500,000, in terms of polystyrene.

[0034] The molecular weight distribution (Mw / Mn), which is the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) measured by gel permeation chromatography (GPC), is preferably in the range of 1.0 to 3.5, more preferably 1.2 to 3.0, and even more preferably 1.5 to 2.8.

[0035] The Mw / Mn and Mw of the 4-methyl-1-pentene copolymer (A) can be adjusted to fall within the above ranges, for example, by using a metallocene catalyst. Mw and Mw / Mn can be determined by analyzing the chromatogram obtained by measuring at a flow rate of 1.0 ml / min and 140°C using a Waters ALC / GPC 150-C plus liquid chromatograph (integrated with a differential refractometer detector) with two Tosoh GMH6-HT columns and two GMH6-HTL columns connected in series, o-dichlorobenzene as the mobile phase medium, and a calibration curve using standard polystyrene samples.

[0036] <Requirements (Ah)> The melt flow rate (MFR; according to ASTM D1238, temperature 230°C, load 2.16 kg) is preferably 0.1 to 100 g / 10 min, more preferably 0.5 to 50 g / 10 min, and even more preferably within the range of 1.0 to 30 g / 10 min.

[0037] When the melt flow rate (MFR) of the 4-methyl-1-pentene copolymer (A) is equal to or greater than the lower limit of the above range, good dispersibility of the flame retardant can be obtained. When it is equal to or less than the upper limit of the above range, the molecular weight of the copolymer (A) is not too low, and a molded article having sufficient mechanical strength can be obtained, which is preferable.

[0038] <Method for producing 4-methyl-1-pentene copolymer (A)> The method for producing the 4-methyl-1-pentene copolymer (A) according to the present invention is not particularly limited, and it can be produced, for example, by polymerizing 4-methyl-1-pentene and the above-mentioned α-olefin having 2 to 4 carbon atoms in the presence of an appropriate polymerization catalyst such as a magnesium-supported titanium catalyst or a metallocene catalyst.

[0039] Suitable polymerization catalysts that can be used here include conventionally known catalysts, such as magnesium-supported titanium catalysts, and metallocene catalysts described in International Publication Nos. 01 / 53369, 01 / 27124, JP-A-3-193796, JP-A-2-41303, JP-A-2011 / 055803, JP-A-2014 / 050817, etc. Polymerization can be carried out by a method appropriately selected from liquid phase polymerization methods including solution polymerization and suspension polymerization, and gas phase polymerization methods.

[0040] In the liquid phase polymerization method, an inert hydrocarbon solvent can be used as a solvent constituting the liquid phase. Examples of the inert hydrocarbon include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, trichloromethane, and tetrachloromethane, and mixtures thereof.

[0041] Furthermore, in the liquid phase polymerization method, bulk polymerization can also be performed using the monomer corresponding to the structural unit (i) derived from the aforementioned 4-methyl-1-pentene (i.e., 4-methyl-1-pentene) or the monomer corresponding to the structural unit (ii) derived from the aforementioned α-olefin having 2 to 4 carbon atoms (i.e., the aforementioned α-olefin having 2 to 4 carbon atoms) itself as a solvent.

[0042] Furthermore, by copolymerizing the above 4-methyl-1-pentene with the above α-olefin having 2 to 4 carbon atoms in a stepwise manner, it is also possible to appropriately control the composition distribution of the 4-methyl-1-pentene structural units (i) and the α-olefin structural units (ii) constituting the 4-methyl-1-pentene copolymer (A).

[0043] The polymerization temperature is preferably −50 to 200° C., more preferably 0 to 100° C., and further preferably 20 to 100° C. The polymerization pressure is preferably normal pressure to 10 MPa gauge pressure, and more preferably normal pressure to 5 MPa gauge pressure.

[0044] During polymerization, hydrogen may be added for the purpose of controlling the molecular weight and polymerization activity of the resulting polymer. The appropriate amount of hydrogen to be added is about 0.001 to 100 nL per 1 kg of the total amount of the 4-methyl-1-pentene and the α-olefin having 2 to 4 carbon atoms.

[0045] <Flame retardant (B)> The flame retardant (B), which is one of the components of the copolymer composition (X) of the present invention, is not particularly limited, and various known flame retardants can be used.

[0046] Among these flame retardants, those containing a phosphate group (phosphorus-based flame retardants) are preferred. Phosphorus-based flame retardants are thought to produce a polyphosphate compound to form a heat-resistant film when the compounded composition is exposed to high temperatures, and also to exert their flame retardant effect through a mechanism that promotes carbonization due to the solid acid.

[0047] Known phosphorus-based flame retardants can be used without limitation. Specific examples include simple phosphorus such as red phosphorus; phosphates such as calcium phosphate and titanium phosphate; phosphate esters such as tributyl phosphate and triphenyl phosphate; polyphosphoric acid; polyphosphates such as calcium polyphosphate; polyphosphate esters such as poly(diphenyl phosphate); phosphine oxides such as triphenylphosphine oxide; phosphoranes such as phenylphosphorane; phosphonic acids such as diphenylphosphonic acid; and phosphine sulfides.

[0048] Among these phosphorus-based flame retardants, phosphorus alone, phosphates, polyphosphoric acid and polyphosphates are preferred because they have a greater flame retarding effect. The flame retardant (B) according to the present invention is more preferably a compound having two or more phosphate groups, even more preferably a polyphosphate, and particularly preferably melamine polyphosphate.

[0049] <Copolymer composition (X)> The copolymer composition (X) of the present invention contains 50 to 95 parts by mass, preferably 55 to 90 parts by mass, and more preferably 60 to 80 parts by mass of the copolymer (A) and 5 to 50 parts by mass, preferably 10 to 45 parts by mass, and more preferably 20 to 40 parts by mass of the flame retardant (B) (the total of (A) and (B) being 100 parts by mass), and satisfies the following requirements (Xa) and (Xb): When the content of flame retardant (B) is within the above range, sufficient flame retardancy and stress relaxation properties are obtained.

[0050] <Requirement (Xa)> The temperature at which the loss tangent tanδ value determined by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) is maximum in the temperature range of -70 to 180°C (hereinafter also referred to as "tanδ peak temperature") is in the range of 0 to 45°C.

[0051] The lower limit of the tan δ peak temperature is preferably 5° C. or higher, more preferably 10° C. or higher. The upper limit of the tan δ peak temperature is preferably 40° C. or lower, more preferably 35° C. or lower. When the tan δ peak temperature is within the above temperature range, the molded article obtained from the copolymer composition (X) of the present invention exhibits high stress relaxation properties over a wide range of environmental temperatures.

[0052] <Requirements (Xb)> The tan δ peak value, obtained by dynamic viscoelasticity measurement at a temperature range of -70 to 180°C and a frequency of 10 rad / s (1.6 Hz), is 0.5 or more, preferably 0.8 or more, and more preferably 1.0 or more. A tan δ peak value of 0.5 or more has an excellent ability to dissipate energy when stress is applied, and the resulting molded article has improved stress relaxation and stress absorption. The higher the tan δ peak value, the greater the above-mentioned effects, so there is no particular upper limit, but the range obtained by normal measurement is 4.0 or less.

[0053] The tan δ peak value obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) is 0.5 or more, preferably 0.8 or more, and more preferably 1.0 or more. A tan δ peak value of 0.5 or more has excellent ability to dissipate energy when stress is applied, and the resulting molded article has improved stress relaxation and stress absorption. The higher the tan δ peak value, the greater the above-mentioned effects, so there is no particular upper limit, but the range obtained by normal measurement is 4.0 or less.

[0054] The copolymer composition (X) of the present invention may contain, in addition to the copolymer (A) and the flame retardant (B), various known additives, such as softeners, release agents, antioxidants, ultraviolet absorbers, surfactants, antistatic agents, pigments, dyes, slip agents, weather resistance stabilizers, heat stabilizers, infrared absorbers, antiblocking agents, antifogging agents, lubricants, plasticizers, antioxidants, hydrochloric acid absorbers, crystal nucleating agents, antifungals, antibacterial agents, and organic fillers, or polymers other than the copolymer (A), within the scope of the object of the present invention.

[0055] <Polymers other than copolymer (A)> Examples of polymers that can be blended into the copolymer composition (X) of the present invention include olefin polymers; for example, low-density, medium-density, and high-density polyethylene, ultra-high molecular weight polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, poly1-butene, poly4-methyl-1-pentene, poly3-methyl-1-butene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, 1-butene-α-olefin copolymer, cyclic olefin copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, and ethylene-unsaturated carboxylic acid copolymer; for example, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, and ethylene-methacrylic acid copolymer. carboxylic acid copolymers, ethylene-unsaturated carboxylic acid ester copolymers; for example, ethylene-(meth)acrylic acid ester copolymers, ethylene-crotonate ester copolymers, ethylene-methyl (meth)acrylate, ethylene-ethyl (meth)acrylate, ethylene-n-butyl (meth)acrylate, ethylene-isobutyl (meth)acrylate, ethylene-cyclohexyl (meth)acrylate copolymers, ethylene-glycidyl (meth)acrylate copolymers, ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid ester copolymers; for example, ethylene-vinyl acetate-glycidyl (meth)acrylate copolymers, ethylene-(meth)acrylic acid-glycidyl (meth)acrylate copolymers, ionomers, styrene-based resins;For example, polystyrene, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, styrene-butadiene copolymer and its hydrogenated products, styrene-isoprene copolymer and its hydrogenated products, styrene-isobutylene copolymer, styrene-isobutylene-styrene block copolymer, styrene-acrylonitrile copolymer, ABS resin, ACS resin, AES resin, ASA resin, fluorine-based resin, rosin-based resin, terpene-based resin and petroleum resin, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, polyacrylonitrile, polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate Examples of suitable polymers include acrylate, polylactic acid, polycaprolactone, polybutylene succinate, polyamino acid, polydimethylsiloxane, polytetramethylene glycol, polyhydroxyethyl methacrylate, polyphenylene terephthalamide, polyacrylamide, polyurethane, polyamide, polyoxymethylene, polycarbonate, polyphenylene ether, polyphenylene sulfide, polysulfone, polyether ether ketone, polyether ketone, polyethylene oxide, polymethyl methacrylate, polyimide, liquid crystal polymer, polyamideimide, polyaminobismaleimide, polyarylate, polyetherimide, polyketone, polybenzimidazole, silicone resin, polybutadiene, cellulose resin, and mixtures of these polymers. These polymers may be composed of one or more types of polymers. Among these polymers, olefin polymers (olefin resins) are preferred.

[0056] The polymer is not limited to an unmodified polymer, but may also be a modified polymer. When the copolymer composition (X) of the present invention contains a polymer other than the copolymer (A), the content thereof is preferably less than 25% by mass based on the total amount of the copolymer composition (X) of the present invention.

[0057] <Softener> Examples of softeners that can be incorporated into the copolymer composition (X) of the present invention include known softeners such as process oil, lubricating oil, paraffin, liquid paraffin, polyolefin waxes such as polyethylene wax and polypropylene wax, petroleum-based substances including petroleum asphalt and Vaseline, coal tars including coal tar and coal tar pitch, fatty oils including castor oil, linseed oil, rapeseed oil, soybean oil and coconut oil, waxes including tall oil, beeswax, carnauba wax and lanolin, fatty acids or metal salts thereof including ricinoleic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, montanic acid, oleic acid and erucic acid, synthetic polymers including petroleum resin, coumarone-indene resin and atactic polypropylene, ester-based plasticizers including dioctyl phthalate, dioctyl adipate and dioctyl sebacate, microcrystalline wax, liquid polybutadiene or modified or hydrogenated products thereof, and liquid thiokol.

[0058] Further examples of the softening agent include aromatic carboxylic acid esters (dibutyl phthalate, etc.), aliphatic carboxylic acid esters (methyl acetylricinoleate, etc.), aliphatic dialkoxy esters (adipic acid-propylene glycol polyester, etc.), aliphatic tricarboxylic acid esters (triethyl citrate, etc.), phosphate triesters (triphenyl phosphate, etc.), epoxy fatty acid esters (epoxybutyl stearate, etc.), and petroleum resins.

[0059] The polyolefin wax may be a modified wax (modified polyolefin wax), and among these, modified polyolefin wax is preferred because it can easily knead the copolymer (A) and the flame retardant (B) since aggregation of the flame retardant (B) in the copolymer (A) is suppressed when the copolymer (A) and the flame retardant (B) are kneaded.

[0060] The type of modified polyolefin wax is not particularly limited, but modified polyethylene wax and modified polypropylene wax are preferred, and modified polyethylene wax is more preferred. The modified polyolefin wax can be produced by known methods. For example, a method of adding an unsaturated carboxylic acid or its derivative to a polyolefin wax by radical reaction in the absence or presence of a Lewis acid, or a method of adding at high temperature, can be used. The reaction temperature is 20°C to 300°C, and preferably 120°C to 250°C.

[0061] <Release agent> Examples of the release agent that can be blended in the copolymer composition (X) of the present invention include lower alcohol esters (having 1 to 4 carbon atoms) of higher fatty acids (butyl stearate, etc.), polyhydric alcohol esters (having 4 to 30 carbon atoms) of fatty acids (hydrogenated castor oil, etc.), glycol esters of fatty acids, and liquid paraffin.

[0062] <Antioxidants> Examples of antioxidants that can be incorporated into the copolymer composition (X) of the present invention include phenol-based antioxidants (2,6-di-t-butyl-4-methylphenol, etc.), polycyclic phenol-based antioxidants (2,2'-methylenebis(4-methyl-6-t-butylphenol) and other methylene-bridged polycyclic phenols, etc.), phosphorus-based antioxidants (tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylenediphosphonate, etc.), and amine-based antioxidants (N,N-diisopropyl-p-phenylenediamine, etc.).

[0063] <Ultraviolet absorber> Examples of ultraviolet absorbents that can be incorporated into the copolymer composition (X) of the present invention include benzotriazole-based, benzophenone-based, salicylic acid-based, and acrylate-based absorbents. Examples of antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, and organic iodines.

[0064] <Surfactants> Surfactants that can be incorporated into the copolymer composition (X) of the present invention include, for example, nonionic, anionic, cationic, or amphoteric surfactants. Examples of nonionic surfactants include polyethylene glycol-based nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; polyhydric alcohol-based nonionic surfactants such as polyethylene oxide, glycerin fatty acid esters, pentaerythritol fatty acid esters, sorbitol or sorbitan fatty acid esters, polyhydric alcohol alkyl ethers, and alkanolamine fatty amides. Examples of anionic surfactants include sulfate ester salts such as alkali metal salts of higher fatty acids; sulfonates such as alkylbenzenesulfonates, alkylsulfonates, and paraffin sulfonates; and phosphate ester salts such as higher alcohol phosphate ester salts. Examples of cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of amphoteric surfactants include amino acid type amphoteric surfactants such as higher alkylaminopropionates, and betaine type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine.

[0065] <Antistatic Agent> Examples of antistatic agents that can be incorporated into the copolymer composition (X) of the present invention include the above-mentioned surfactants, fatty acid esters, and polymeric antistatic agents. Examples of fatty acid esters include esters of stearic acid and oleic acid, and examples of polymeric antistatic agents include polyetheresteramides.

[0066] Pigments and dyes Examples of pigments and dyes that can be blended into the copolymer composition (X) of the present invention include inorganic pigments (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake pigments, thioindigo pigments, phthalocyanine pigments, anthraquinone pigments). Examples of dyes include azo pigments, anthraquinone pigments, and triphenylmethane pigments. The amount of these pigments and dyes added is not particularly limited, but is usually 5 parts by mass or less, preferably 0.1 to 3 parts by mass, per 100 parts by mass of the copolymer composition of the present invention.

[0067] <Slip agent> Examples of slip agents that can be blended in the copolymer composition (X) of the present invention include waxes (carnauba wax, etc.), higher fatty acids (stearic acid, etc.), higher fatty acid salts (calcium stearate, etc.), higher alcohols (stearyl alcohol, etc.), and higher fatty acid amides (stearamide, erucamide, etc.).

[0068] <Method for producing copolymer composition (X)> The method for producing the copolymer composition (X) of the present invention is not particularly limited, and for example, a conventionally known production method can be used. Examples of the method include a method of dry-blending the copolymer (A) and flame retardant (B) constituting the copolymer composition (X) of the present invention, and, if necessary, the various known additives or polymers, using a known mixer, specifically, for example, a Henschel mixer, a tumbler blender, or a V-blender, or a method of dissolving them in a solvent and solution-mixing them.

[0069] After dry blending in the mixer, the components can be melt-kneaded at a temperature of 100 to 270°C using a single-screw extruder, twin-screw extruder, Banbury mixer, kneader, roll mill, or the like, followed by granulation or pulverization. Among these, melt-kneading using a twin-screw extruder or Banbury mixer is preferred from the viewpoints of the mixability of the components and productivity. These methods can produce pellets of high-quality copolymer composition (X) in which the components are uniformly mixed and dispersed.

[0070] As a method for producing the copolymer composition (X) of the present invention, particularly preferably, after melt-mixing at a temperature not lower than the temperature at which the flame retardant (B) dissolves in the melted copolymer (A), it is solidified by cooling to obtain a solid material such as pellets.

[0071] The temperature not lower than the temperature at which the flame retardant (B) dissolves in the melted copolymer (A) may be any temperature at which the effect of the present invention is exhibited, and it is not necessarily required that 100% of the flame retardant (B) dissolves. For example, it means the temperature at which 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more of the contained flame retardant (B) dissolves.

[0072] Also, from the viewpoint of deterioration such as coloring of the copolymer (A), it is not preferable that the temperature (T1) during melt-mixing is too high. For example, it is recommended that the temperature be within the following range. Tm≦T1<Tm + 15 ··· (Formula 1) *Tm is the temperature at which the flame retardant (B) blended dissolves in the melted copolymer (A).

[0073] <Molded article> Examples of the molded article containing the copolymer composition (X) of the present invention include sheets, films, injection molded articles, and the like.

[0074] The method for producing the molded article of the present invention is not particularly limited. For example, conventionally known production methods can be used, and examples include extrusion molding, compression molding, injection molding, 3D printing, and microwave heating molding. Among such molding methods, the molded article can be preferably produced by extrusion molding.

[0075] Furthermore, when a sheet-like molded product is desired, extrusion sheet molding using a general T-die is preferred. A sheet can be produced by film formation using a single-screw extruder or twin-screw extruder equipped with a T-die at a cylinder temperature of 180 to 250°C and a casting roll temperature of 20 to 80°C. The thickness of the sheet will vary depending on the application, but is usually 10 to 1000 μm, preferably 20 to 500 μm, so that pinholes do not occur during sheet molding, sufficient mechanical strength is obtained, and it is advantageous for mass production of sheets.

[0076] The surface of the sheet may be embossed, and the sheet may be stretched during or after molding. Furthermore, in order to remove residual stress from the sheet, the sheet may be annealed at a temperature below the melting point of the resin.

[0077] The molded article containing the copolymer composition (X) of the present invention may be a multilayer film, and the copolymer composition (X) of the present invention may be contained in one layer constituting the multilayer film. The laminate containing the copolymer composition (X) of the present invention may be stretched uniaxially or biaxially. A preferred method for uniaxial stretching is the commonly used roll stretching method. Examples of biaxial stretching methods include a sequential stretching method in which uniaxial stretching is followed by biaxial stretching, and a simultaneous biaxial stretching method such as a tubular stretching method.

[0078] <Application> The copolymer composition (X) of the present invention and a molded article containing the composition have high stress relaxation properties, vibration absorption properties, and flame retardancy, and therefore can be used in conventionally known applications such as automotive materials, clothing materials, sanitary materials, construction materials, shoe materials, sporting materials, leisure materials, and industrial materials.

[0079] Examples of applications of the laminate include industrial release films, semiconductor process films, and surface protection films. Furthermore, the film can also be suitably used for films or tapes used in the electronics field, such as adhesive films, protective films, semiconductor process protective films, lens protective films, backgrinding tapes for semiconductor wafers, dicing tapes, and substrate protective tapes (e.g., protective tapes for plating masks used in plating processes for flexible printed circuit boards); window glass protective films; and baked coating films.

[0080] Furthermore, the adhesive layer (L1) has the ability to conform to irregularities, and is therefore suitable for use in prism sheets and reflective sheets with many irregularities on the surface, as well as sheets for protecting textured surfaces.

[0081] Specifically, the film can be suitably used as a surface protection film for protecting adherends such as metal members made of aluminum, steel, stainless steel, etc., members made of these metal members coated with paint, glass members, synthetic resin members, and further, home appliances, automobile parts, electronic parts, etc., which use these members.

[0082] Furthermore, the copolymer composition (X) and a molded article containing the composition are also useful as heat radiation members in applications requiring high thermal conductivity and flame retardancy, such as electronic components for devices requiring high thermal conductivity and flame retardancy, heat radiation members for various electronic devices such as laptops, mobile phones, home game consoles, VR devices, and home appliances, and heat radiation members for battery packs such as alkaline batteries, manganese batteries, lithium-ion batteries, lead batteries, nickel-cadmium batteries, nickel-metal hydride batteries, and automotive batteries. [Example]

[0083] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the methods for measuring the physical properties of the polymer, the polymers used, the method for preparing test pieces, and the evaluation methods are as follows.

[0084] Methods for measuring polymer properties 〔composition〕 The content (mol%) of each structural unit (4-methyl-1-pentene and α-olefin) in the 4-methyl-1-pentene copolymer (A) is 13 Measurement was performed by C-NMR. Measurement equipment: Nuclear magnetic resonance equipment (ECP500 model, manufactured by JEOL Ltd.) Observation core: 13 C(125MHz) Sequence: Single pulse proton decoupling Pulse width: 4.7 μsec (45° pulse) Repeat time: 5.5 seconds Accumulation count: 10,000 times or more Solvent: orthodichlorobenzene / deuterated benzene (volume ratio: 80 / 20) mixed solvent Sample concentration: 55mg / 0.6mL ·Measurement temperature: 120℃ Chemical shift reference value: 27.50 ppm

[0085] [Intrinsic viscosity [η]] The intrinsic viscosity [η] of the polymer was measured by the method described above.

[0086] [Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)] The weight-average molecular weight (Mw) of the polymer and the molecular weight distribution (Mw / Mn), which is the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). Measurement equipment: GPC (ALC / GPC 150-C plus type, differential refractometer detector integrated, manufactured by Waters) Column: Two GMH6-HT (Tosoh Corporation) and two GMH6-HTL (Tosoh Corporation) columns connected in series Eluent: o-dichlorobenzene Column temperature: 140℃ Flow rate: 1.0mL / min

[0087] [Melt flow rate (MFR)] Measured in accordance with ASTM D1238 at 230°C under a load of 2.16 kg. The unit is g / 10 min.

[0088] 〔density〕 The density of the polymer was measured in accordance with JIS K7112 (density gradient tube method). [Melting point (Tm)] The melting point (Tm) of the polymer was measured using a differential scanning calorimeter (DSC220C, manufactured by Seiko Instruments Inc.). Approximately 5 mg of polymer was sealed in a measurement aluminum pan and heated from room temperature to 200°C at 10°C / min. To completely melt the polymer, the pan was held at 200°C for 5 minutes and then cooled to -50°C at 10°C / min. After leaving the pan at -50°C for 5 minutes, the pan was heated a second time to 200°C at 10°C / min, and the peak temperature (°C) at this second heating was taken as the melting point (Tm) of the polymer. If multiple peaks were detected, the peak detected at the highest temperature was used.

[0089] <Method of producing sheets for various measurements> Sheets were formed at a gauge pressure of 10 MPa using a Shinto Metal Industries hydraulic heat press (NS-50) set to 180°C. For 1-3 mm thick sheets (spacer shape: 200 x 200 x 1-3 mm on a 240 x 240 mm plate), the sheets were preheated for 5-7 minutes, pressed at a gauge pressure of 10 MPa for 1-2 minutes, and then compressed at a gauge pressure of 10 MPa using another Shinto Metal Industries hydraulic heat press set to 20°C. The sheets were then cooled for approximately 5 minutes to prepare the measurement samples. A 5 mm thick brass plate was used as the heating plate. The samples prepared using the above method were used to evaluate various physical properties.

[0090] [Dynamic viscoelasticity] Dynamic viscoelasticity measurements were performed using a 3 mm thick pressed sheet of the polymer or copolymer composition to be measured as the measurement sample, and then cutting out 45 mm x 10 mm x 3 mm strips required for dynamic viscoelasticity measurements. Using an ANTON Paar MCR301, the temperature dependence of dynamic viscoelasticity was measured from -70 to 180°C at a frequency of 10 rad / s (1.6 Hz). The temperature at which the loss tangent (tanδ) due to the glass transition temperature reached its peak value (maximum value) in the range of 0 to 40°C (hereinafter referred to as the "peak value temperature") and the value of the loss tangent (tanδ) at that time were measured.

[0091] [Mechanical properties: tensile strength, tensile elongation] The tensile strength and tensile elongation of the molded articles were measured by tensile testing using dumbbell-shaped molded article specimens in accordance with ASTM D638 Type 4. The dumbbell-shaped molded article specimens were prepared by punching out 130 mm × 130 mm × 2 mm thick flat molded articles (sheets) obtained by the method described above in "Method for preparing sheets for various measurements." Tensile testing was performed using a five-arm tensile testing machine, Model 2005X-5, manufactured by Intesco Corporation, at 23°C and a test speed of 50 mm / min in accordance with ASTM D638.

[0092] [Electrical characteristics] A 50 mm x 50 mm x 0.5 mm thick sheet of the polymer or copolymer composition to be measured was used as the measurement sample. The sheet was placed in a cylindrical cavity resonator (material: copper, internal mirror finish), and a 10 GHz electrical signal was output using a YHP Synthesized Sweeper 8340B. The dielectric constant and dielectric loss around 10 GHz were measured using a Network Analyzer 8510B.

[0093] [Flame retardancy] A 125mm x 13.3mm x 1.8mm thick sheet made of the polymer or copolymer composition to be measured was used as the measurement sample. After leaving the sample at 23°C and 50% humidity for at least 48 hours, the test piece was held horizontally and exposed to a flame for 30 seconds using an Atlas UL combustion test chamber. The flame retardancy was then evaluated based on the burning rate from the 25mm mark to the 100mm mark. Measurements were carried out three times each. The test passed if the burning condition was A to C below. Burning condition: A: If the tip of the flame does not exceed the 25mm mark. B: The tip of the flame passes the 25mm mark but goes out before the 100mm mark. C: When the tip of the flame passes the 100mm mark, the burning speed between the 25mm and 100mm marks does not exceed 76.2mm per minute.

[0094] [Polymer] <Synthesis Example 1> <Synthesis of 4-methyl-1-pentene copolymer (A-1)> A 1.5 L stainless steel autoclave equipped with a stirrer and thoroughly purged with nitrogen was charged with 300 ml of n-hexane (dried over activated alumina under a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene at 23° C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was charged into the autoclave, and the stirrer was turned on.

[0095] Next, the autoclave was heated until the internal temperature reached 60°C, and pressurized with propylene to a total pressure (gauge pressure) of 0.40 MPa. Next, 0.34 ml of a toluene solution containing 1 mmol of methylaluminoxane (calculated as Al) and 0.01 mmol of diphenylmethylene(1-ethyl-3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride, which had been prepared in advance, was injected into the autoclave with nitrogen pressure to initiate the polymerization reaction. During the polymerization reaction, the internal temperature of the autoclave was adjusted to 60°C.

[0096] Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to terminate the polymerization reaction, and the pressure inside the autoclave was then reduced to atmospheric pressure. After the pressure was reduced, acetone was added to the reaction solution while stirring the reaction solution, thereby obtaining a polymerization reaction product containing the solvent.

[0097] The resulting solvent-containing polymerization reaction product was then dried under reduced pressure at 100°C for 12 hours to obtain 36.9g of a powdery 4-methyl-1-pentene copolymer (A-1) (hereinafter referred to as "copolymer (A-1)"). The measurement results of various physical properties of the resulting copolymer (A-1) are shown in Table 1.

[0098] The content of 4-methyl-1-pentene in copolymer (A-1) was 72.5 mol %, and the content of propylene was 27.5 mol %. The density of copolymer A-1 was 839 kg / m 3 The copolymer (A-1) had an intrinsic viscosity [η] of 1.5 dl / g, a weight average molecular weight (Mw) of 337,000, a molecular weight distribution (Mw / Mn) of 2.1, and a melt flow rate (MFR) of 11 g / 10 min. The melting point (Tm) of the copolymer (A-1) was not observed.

[0099] [Table 1]

[0100] [Flame retardant (B)] The following flame retardants (B) were used: <Flame retardant (B-1)> Sanwa Chemical Co., Ltd.: Grade MPP-A (generic name: melamine polyphosphate)

[0101] [4-methyl-1-pentene polymer (E-2)] 4-Methyl-1-pentene-1-hexadecene-1-octadecene copolymer (E-2) (hereinafter "copolymer (E-2)") was obtained by varying the ratios of 4-methyl-1-pentene, 1-decene, 1-hexadecene, 1-octadecene, and hydrogen in accordance with the polymerization methods described in Comparative Examples 7 and 9 of WO 2006 / 054613. The melt flow rate (MFR) of copolymer (E-2) measured at 260°C and 5 kgf was 21 g / 10 min, the tan δ peak temperature was 30°C, and the melting point was 224°C.

[0102] [Example 1] 70 parts by mass of copolymer (A-1) and 30 parts by mass of flame retardant (B-1) were blended and granulated using a single-screw extruder (product name: Thermo 20mm single-screw extruder, manufactured by Thermo Plastics Industries Co., Ltd., screw diameter 20mmφ, L / D=28) at a set temperature of 200°C, a resin extrusion rate of 16.6g / min and 75rpm to obtain a pellet-shaped copolymer composition. The copolymer composition obtained was heated at 190°C for 5 minutes using a hot press, and then cooled and pressed to obtain a pressed sheet having a thickness of 2 mm. The physical properties of the obtained sheet are shown in Table 2.

[0103] [Example 2] A sheet was obtained in the same manner as in Example 1, except that 60 parts by mass of copolymer (A-1) and 40 parts by mass of flame retardant (B-1) were blended. Various physical properties of the obtained sheet are shown in Table 2. In the above-mentioned flame retardancy test, two of the three tests conducted were rated A and the remaining one was rated B.

[0104] [Comparative Example 1] A sheet was obtained in the same manner as in Example 1, except that an olefin-based elastomer (E-1) (trade name Vistamaxx 6202, manufactured by Exxon-Mobil, MFR: 20 g / 10 min (230°C, 2.16 kgf), tan δ peak temperature: -22°C) was used instead of the copolymer (A-1) used in Example 1. The physical properties of the obtained sheet are shown in Table 2.

[0105] Comparative Example 2 A sheet was obtained in the same manner as in Example 1, except that only the copolymer (A-1) was used instead of the copolymer composition obtained in Example 1. The physical properties of the obtained sheet are shown in Table 2.

[0106] Comparative Example 3 A sheet was obtained in the same manner as in Example 1, except that copolymer (E-2) was used instead of copolymer (A-1) used in Example 1. Various physical properties of the obtained sheet are shown in Table 2.

[0107] [Table 2]

Claims

1. A copolymer composition (X) containing 60 to 80 parts by mass of a 4-methyl-1-pentene copolymer (A) satisfying at least one of the following requirements (A-a) and (A-b), and 20 to 40 parts by mass of a flame retardant (B) (the total of (A) and (B) being 100 parts by mass), and satisfying the following requirements (X-a) and (X-b): Requirement (A-a) The copolymer is composed of 60 to 97 mol % of structural units (i) derived from 4-methyl-1-pentene and 3 to 40 mol % of structural units (ii) derived from an α-olefin having 2 to 4 carbon atoms (the total of structural units (i) derived from 4-methyl-1-pentene and structural units (ii) derived from an α-olefin having 2 to 4 carbon atoms being 100 mol %); Requirement (A-b): The melting point measured by a differential scanning calorimeter (DSC) is 160°C or less, or no melting point is observed; Requirement (X-a) The tan δ peak temperature, as determined by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in a temperature range of -70 to 180°C, is in the range of 0 to 45°C; Requirement (Xb): The tan δ peak value obtained by measuring dynamic viscoelasticity at a frequency of 10 rad / s (1.6 Hz) in a temperature range of −70 to 180° C. is 0.5 or more.

2. The copolymer composition (X) according to claim 1, wherein the flame retardant (B) has a phosphate group.

3. The copolymer composition (X) according to claim 2, wherein the flame retardant (B) has two or more phosphate groups.

4. A pellet comprising the copolymer composition (X) according to any one of claims 1 to 3.

5. A molded article comprising the copolymer composition (X) according to any one of claims 1 to 3.

6. A film or sheet comprising the copolymer composition (X) according to any one of claims 1 to 3.

7. A heat radiation member comprising the copolymer composition (X) according to any one of claims 1 to 3.

Images