JP4788510B2 - Resin composition, waterproof sheet and method for producing waterproof sheet - Google Patents

Description

  The present invention relates to an ethylene-based resin composition for waterproof sheets, a waterproof sheet comprising the resin composition, and a method for producing the waterproof sheet.

  Waterproof sheets used for water stoppages such as ornamental ponds, rooftops of houses, and landfills are required to have mechanical strength, flexibility, heat resistance, etc. Has been used a lot. For example, a waterproof sheet (for example, refer to Patent Document 1) formed by T-die molding a resin composition obtained by blending a flame retardant with an ethylene-vinyl acetate copolymer, a commercially available ethylene-produced with a metallocene catalyst. A waterproof sheet (for example, refer to Patent Document 2) formed by T-die molding of a resin composition obtained by adding silica to a 1-octene copolymer has been proposed.

Japanese Patent Laid-Open No. 3-58839 JP-A-9-157456

However, the conventional ethylene-based resin composition for waterproof sheets is sufficiently satisfactory in workability because the resin composition may stick to the roll or the sheet taken off from the roll may drip when calendering the waterproof sheet. It wasn't going. Further, when a flame retardant waterproof sheet was prepared by blending a flame retardant, the balance between the mechanical strength and the heat resistance of the waterproof sheet was not sufficiently satisfactory.
Under such circumstances, the problem to be solved by the present invention is that a flame retardant waterproof sheet excellent in balance between mechanical strength and heat resistance is obtained, and a resin composition for a waterproof sheet excellent in calendar workability, It is providing the waterproof sheet which consists of this resin composition, and the manufacturing method of this waterproof sheet.

That is, the first of the present invention contains the following components (A), (B) and (C), the total amount of the components (A) and (B) is 100% by weight, and the content of the component (A) Is 90 to 40% by weight, the content of component (B) is 10 to 60% by weight, and the content of component (C) is 0 per 100 parts by weight of the total amount of component (A) and component (B). 0.1 to 200 parts by weight of the resin composition for waterproof sheets.
(A): The flow activation energy (Ea) is 40 kJ / mol or more, and the melt flow rate (MFR) measured under conditions of a temperature of 190 ° C. and a load of 21.18 N specified in JIS K7210 is 0.1. Ethylene-α-olefin copolymer (B) having a molecular weight distribution (Mw / Mn) of 5 to 25: ethylene having a flow activation energy (Ea) of less than 40 kJ / mol α-olefin copolymer (C): flame retardant

  The second of the present invention relates to a waterproof sheet comprising the above resin composition.

  A third aspect of the present invention relates to a method for producing a waterproof sheet in which the resin composition is calendered.

  According to the present invention, a flame retardant waterproof sheet excellent in balance between mechanical strength and heat resistance is obtained, and a resin composition for a waterproof sheet excellent in calendar processability, a waterproof sheet comprising the resin composition, and the A method for manufacturing a waterproof sheet can be provided. Moreover, the waterproof sheet of the present invention is excellent in flame retardancy and has a good balance between flexibility and heat resistance.

  The component (A) ethylene-α-olefin copolymer of the present invention is an ethylene-α-olefin copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4 -Methyl-1-pentene, 4-methyl-1-hexene and the like can be mentioned, and 1-butene, 1-hexene and 1-octene are preferable. Moreover, said C3-C20 alpha olefin may be used independently and may use 2 or more types together.

  Examples of the ethylene-α-olefin copolymer of component (A) include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer. Preferred are ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-butene-1-hexene copolymer, ethylene-1-butene-1-octene copolymer. It is a coalescence.

  The content of the monomer unit based on ethylene in the ethylene-α-olefin copolymer of the component (A) is usually from 50 to 50% based on the total weight (100% by weight) of the ethylene-α-olefin copolymer. 99% by weight. The content of the monomer unit based on the α-olefin having 3 to 20 carbon atoms is usually 1 to 50% by weight with respect to the total weight (100% by weight) of the ethylene-α-olefin copolymer.

  The ethylene-α-olefin copolymer of component (A) has a long chain branch, and such an ethylene-α-olefin copolymer is a conventional ethylene-α-olefin copolymer that has been used for water-stop sheets. Compared with a polymer, the flow activation energy (Ea) is high, and is usually 40 kJ / mol or more. The Ea of the ethylene-α-olefin copolymer that has been used in conventionally known water-stop sheets is usually lower than 40 kJ / mol.

  The flow activation energy (Ea) of the ethylene-α-olefin copolymer of component (A) is preferably 45 kJ / mol or more, more preferably 50 kJ / mol or more, from the viewpoint of improving calendar processability. More preferably, it is 60 kJ / mol or more. Further, from the viewpoint of increasing the mechanical strength, the Ea is preferably 100 kJ / mol or less, more preferably 90 kJ / mol or less.

The activation energy (Ea) of the flow of the ethylene-α-olefin copolymer (A) is an angular frequency (unit: Pa · sec) at 190 ° C. based on the temperature-time superposition principle. (Unit: rad / sec) It is a numerical value calculated by the Arrhenius equation from the shift factor (a _T ) at the time of creating a master curve showing dependency, and is a value obtained by the following method. That is, an ethylene-α-olefin copolymer at each temperature (T, unit: ° C.) for four temperatures including 190 ° C. among temperatures of 130 ° C., 150 ° C., 170 ° C., 190 ° C., and 210 ° C. The melt complex viscosity-angular frequency curve (melt melt viscosity unit is Pa · sec, angular frequency unit is rad / sec) based on the temperature-time superposition principle at each temperature (T). For each melt complex viscosity-angular frequency curve, the shift factor (a _T ) at each temperature (T) obtained when superimposed on the melt complex viscosity-angular frequency curve of the ethylene copolymer at 190 ° C. is obtained. , and each of the temperature (T), a first-order approximation of from shift factor and (a _T), by the method of least squares and [ln (a _T)] and [1 / (T + 273.16) ] at each temperature (T) Formula (Formula (I) below) is calculated. Next, Ea is obtained from the slope m of the linear expression and the following expression (II).
ln (a _T ) = m (1 / (T + 273.16)) + n (I)
Ea = | 0.008314 × m | (II)
a _T : Shift factor Ea: Activation energy of flow (unit: kJ / mol)
T: Temperature (unit: ° C)
For the calculation, commercially available calculation software may be used. As the calculation software, Rheos V. manufactured by Rheometrics is used. 4.4.4.
The shift factor (a _T ) is obtained by moving the logarithmic curve of the melt complex viscosity-angular frequency at each temperature (T) in the log (Y) = − log (X) axis direction (however, the Y axis Is the complex viscosity of the melt, and the X axis is the angular frequency.), And the amount of movement when superposed on the melt complex viscosity-angular frequency curve at 190 ° C., in the superposition, melting at each temperature (T) The logarithmic curve of complex viscosity-angular frequency shifts the angular frequency _aT times and the melt complex viscosity 1 / _aT times.
In addition, when obtaining the linear approximation formula (I) obtained from the shift factors and temperatures at four temperatures including 190 ° C. from 130 ° C., 150 ° C., 170 ° C., 190 ° C., and 210 ° C. by the method of least squares. The correlation coefficient is usually 0.99 or more.

  The above-mentioned melt complex viscosity-angular frequency curve is measured using a viscoelasticity measuring apparatus (for example, Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics). Usually, geometry: parallel plate, plate diameter: 25 mm, plate interval: It is performed under the conditions of 1.5 to 2 mm, strain: 5%, angular frequency: 0.1 to 100 rad / sec. The measurement is performed in a nitrogen atmosphere, and it is preferable that an appropriate amount of an antioxidant (for example, 1000 ppm) is blended in advance with the measurement sample.

  The melt flow rate (MFR) of the ethylene-α-olefin copolymer of component (A) is 0.01 to 100 g / 10 min. If the MFR is too low, the motor load of an extruder or the like may increase during molding. Preferably it is 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more. Further, if the MFR is too high, calendar workability may be deteriorated. Preferably it is 10 g / 10 minutes or less, More preferably, it is 5 g / 10 minutes or less, More preferably, it is 3 g / 10 minutes or less, Most preferably, it is 2 g / 10 minutes or less. In addition, this MFR is measured on condition of temperature 190 degreeC and load 21.18N in the method prescribed | regulated to JISK7210-1995.

  The melt flow rate ratio (MFRR) of the ethylene-α-olefin copolymer of component (A) is usually 40 to 300. The MFRR is preferably 50 or more, more preferably 55 or more, from the viewpoint of further improving the calendar workability. The MFRR is preferably 250 or less, more preferably 200 or less, from the viewpoint of further increasing the mechanical strength. The MFRR is a melt flow rate (MFR-H, unit: g / 10 minutes) measured under the conditions of a test load of 211.83 N and a measurement temperature of 190 ° C. in the method defined in JIS K7210-1995. In the method defined in JIS K7210-1995, it is a value divided by the melt flow rate (MFR) measured under conditions of a load of 21.18 N and a temperature of 190 ° C.

The density of the ethylene-α-olefin copolymer of component (A) is usually 880 to 960 kg / m ³ . The density is preferably 940 kg / m ³ or less, more preferably 930 kg / m ³ or less, further preferably 925 kg / m ³ or less, and most preferably, from the viewpoint of further improving mechanical strength and flexibility. Is 920 kg / m ³ or less. Further, the density is preferably 890 kg / m ³ or more, more preferably 900 kg / m ³ or more, from the viewpoint of improving heat resistance. The density is measured according to a method defined in JIS K7112-1980.

  The molecular weight distribution (Mw / Mn) of the ethylene-α-olefin copolymer of the component (A) is preferably 6 or more, more preferably 7 or more, from the viewpoint of improving calendar processability. The Mw / Mn is preferably 25 or less, more preferably 20 or less, and still more preferably 17 or less, from the viewpoint of increasing mechanical strength. The molecular weight distribution (Mw / Mn) is a value obtained by obtaining a weight average molecular weight (Mw) and a number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography, and dividing Mw by Mn ( Mw / Mn).

The ethylene-α-olefin copolymer of component (A) is measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method defined in JIS K7210-1995, from the viewpoint of improving calendar processability and mechanical strength. It is preferable that the melt flow rate is MFR (unit: g / 10 min) and the intrinsic viscosity is [η] (unit: dl / g) to satisfy the following formula (1).
0.80 × MFR ^−0.094 <[η] <1.50 × MFR ^−0.156 Formula (1)
From the viewpoint of increasing mechanical strength, the ethylene-α-olefin copolymer (A) more preferably satisfies the following formula (1-2):
0.90 × MFR ^−0.094 <[η] Formula (1-2)
It is more preferable to satisfy the following formula (1-3).
1.00 × MFR ^−0.094 <[η] Formula (1-3)
Moreover, from the viewpoint of improving calendar processability, the ethylene-α-olefin copolymer of component (A) more preferably satisfies the following formula (1-4),
[Η] <1.40 × MFR ^−0.156 formula (1-4)
It is more preferable that the following formula (1-5) is satisfied.
[Η] <1.35 × MFR ^−0.156 formula (1-5)
In addition, in the method prescribed | regulated to JISK7210-1995, the melt flow rate measured on condition of temperature 190 degreeC and load 21.18N is the same value, and the ethylene of this invention and the ethylene of this invention When comparing with the -α-olefin copolymer, the intrinsic viscosity of the conventional ethylene-α-olefin copolymer is usually higher than the intrinsic viscosity of the ethylene-α-olefin copolymer of the present invention. .

The ethylene-α-olefin copolymer of component (A) is measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method defined in JIS K7210-1995 from the viewpoint of improving calendar moldability and mechanical strength. Preferably, the melt flow rate is MFR (unit: g / 10 min), the melt tension at 190 ° C. is MT (unit: cN), and the following formula (2) is satisfied.
2 x MFR ^-0.59 <MT <20 x MFR ^-0.59 Formula (2)
From the viewpoint of enhancing calendar processability, the ethylene-α-olefin copolymer of component (A) more preferably satisfies the following formula (2-2):
2.2 × MFR ^-0.59 <MT formula (2-2)
It is more preferable to satisfy the following formula (2-3).
2.5 × MFR ^-0.59 <MT formula (2-3)
Further, from the viewpoint of increasing mechanical strength, the ethylene-α-olefin copolymer of component (A) more preferably satisfies the following formula (2-4),
MT <10 × MFR ^-0.59 formula (2-4)
It is more preferable to satisfy the following formula (2-5).
MT <5 × MFR ^-0.59 formula (2-5)

The ethylene-α-olefin copolymer of component (A) has a melt complex viscosity of η ^* (unit: Pa · sec) at a temperature of 190 ° C. and an angular frequency of 100 rad / sec from the viewpoint of improving calendar processability. In the method defined in K7210-1995, a melt flow rate measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N is defined as MFR (unit: g / 10 minutes), and the following formula (3) is preferably satisfied. ,
η ^* <1550 × MFR ^−0.25 −420 Formula (3)
More preferably, the following formula (3-2) is satisfied,
η ^* <1500 × MFR ^−0.25 −420 Formula (3-2)
More preferably, the following formula (3-3) is satisfied,
η ^* <1450 × MFR ^−0.25 −420 Formula (3-3)
It is particularly preferable that the following formula (3-4) is satisfied.
η ^* <1350 × MFR ^−0.25 −420 Formula (3-4)

The melt complex viscosity η ^* is obtained in the measurement of the melt complex viscosity-angular frequency at 190 ° C. among the measurements performed for obtaining the activation energy (Ea) of the flow of the ethylene-α-olefin copolymer (A). The melt complex viscosity at an angular frequency of 100 rad / sec.

  As a method for producing the ethylene-α-olefin copolymer of component (A), for example, a promoter component such as an organoaluminum compound, an organoaluminum oxy compound, a boron compound, and an organozinc compound is supported on a particulate carrier. It has a solid particulate promoter component (hereinafter referred to as component (i)) and a ligand having a structure in which two cyclopentadienyl type anion skeletons are bonded to each other by a crosslinking group such as an alkylene group or a silylene group. Examples thereof include a method in which ethylene and an α-olefin are copolymerized in the presence of a polymerization catalyst using a metallocene complex (hereinafter referred to as component (b)) as a catalyst component.

  Examples of the solid particulate promoter component include a component in which methylalumoxane is mixed with porous silica, a component in which diethyl zinc, water, and fluorinated phenol are mixed with porous silica.

More specific examples of the solid particulate promoter component include component (a) diethylzinc, component (b) fluorinated phenol, component (c) water, component (d) porous silica and component (e) trimethyldisilazane. The promoter support component (a) obtained by contacting (((CH ₃ ) ₃ Si) ₂ NH) can be mentioned.

  Examples of the fluorinated phenol of component (b) include pentafluorophenol, 3,5-difluorophenol, 3,4,5-trifluorophenol, 2,4,6-trifluorophenol and the like. From the viewpoint of increasing the fluid activation energy (Ea) and molecular weight distribution (Mw / Mn) of the component (A), it is preferable to use two types of fluorinated phenols having different fluorine numbers. The molar ratio with the phenol having a small number of fluorine is usually 20/80 to 80/20, and the higher the molar ratio is preferable.

The amount of component (a), component (b) and component (c) used is the molar ratio of the amount of each component used: component (a): component (b): component (c) = 1: y: z Then, it is preferable that y and z satisfy the following formula.
| 2-y-2z | ≦ 1
Y in the above formula is preferably a number of 0.01 to 1.99, more preferably a number of 0.10 to 1.80, and still more preferably a number of 0.20 to 1.50. Most preferably, the number is 0.30 to 1.00.

  The amount of the component (d) used relative to the component (a) is such that the number of moles of zinc atoms contained in the particles obtained by contacting the component (a) and the component (d) is 0.00 per gram of the particles. The amount is preferably 1 mmol or more, and more preferably 0.5 to 20 mmol. The amount of the component (e) to be used with respect to the component (d) is preferably an amount that makes the component (e) 0.1 mmol or more per 1 g of the component (d), and an amount that becomes 0.5 to 20 mmol. More preferably.

  The metallocene complex includes a zirconocene complex in which two indenyl groups are bonded by an ethylene group, a dimethylmethylene group, or a dimethylsilylene group, and a zirconocene in which two methylindenyl groups are bonded by an ethylene group, a dimethylmethylene group, or a dimethylsilylene group. Complex A zirconocene complex in which two methylcyclopentadienyl groups are linked by ethylene, dimethylmethylene or dimethylsilylene groups. Two dimethylcyclopentadienyl groups are linked by ethylene, dimethylmethylene or dimethylsilylene groups. Zirconocene complexes and the like. Moreover, as a metal atom of a component (b), a zirconium and hafnium are preferable, and also as a remaining substituent which a metal atom has, a diphenoxy group and a dialkoxy group are preferable. The component (b) is preferably ethylenebis (1-indenyl) zirconium diphenoxide.

  In the polymerization catalyst comprising the above-described solid particulate promoter component and the metallocene complex, an organoaluminum compound may be used in combination as a catalyst component as appropriate. Examples of the organoaluminum compound include triisobutylaluminum, trinormal Examples include octyl aluminum.

The amount of the metallocene complex used is preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol per 1 g of the solid particulate promoter component. The amount of the organoaluminum compound used is preferably such that the aluminum atom of the organoaluminum compound is 1 to 2000 mol per mol of the metal atom of the metallocene complex.

  In addition, in the polymerization catalyst using the solid particulate promoter component and the metallocene complex, an electron donating compound may be used as a catalyst component as appropriate. Examples of the electron donating compound include triethylamine, Examples thereof include tri-normal octylamine.

  When two types of fluorinated phenols having different numbers of fluorine are used as the component (b) fluorinated phenol, it is preferable to use an electron donating compound.

  The amount of the electron-donating compound used is usually 0.1 to 10 mol% with respect to the number of moles of aluminum atoms in the organoaluminum compound used as the catalyst component, and the molecular weight distribution (Mw / From the viewpoint of increasing Mn), the amount used is preferably higher.

  More specifically, as a method for producing the ethylene-α-olefin copolymer of component (A), a catalyst obtained by contacting the promoter support (a), the crosslinked bisindenylzirconium complex and the organoaluminum compound. In the presence of, there is a method of copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms.

  The polymerization method is preferably a continuous polymerization method involving molding of ethylene-α-olefin copolymer particles, such as continuous gas phase polymerization, continuous slurry polymerization, and continuous bulk polymerization, preferably continuous gas phase. Polymerization. The gas phase polymerization reaction apparatus is usually an apparatus having a fluidized bed type reaction tank, and preferably an apparatus having a fluidized bed type reaction tank having an enlarged portion. A stirring blade may be installed in the reaction vessel.

  As a method for supplying each component of the polymerization catalyst used for the production of the component (A) ethylene-α-olefin copolymer to the reaction vessel, usually, an inert gas such as nitrogen or argon, hydrogen, ethylene or the like is used. Then, a method of supplying in a state free from moisture, or a method of supplying each component in a solution or slurry after dissolving or diluting each component in a solvent is used. Each component of the polymerization catalyst may be supplied individually, or arbitrary components may be supplied in contact in advance in any order.

  Moreover, it is preferable to carry out prepolymerization before carrying out the main polymerization and to use the prepolymerized prepolymerized catalyst component as a catalyst component or catalyst for the main polymerization. Different α-olefins may be used in the main polymerization and the prepolymerization, and it is preferable to prepolymerize the α-olefin having 4 to 12 carbon atoms with ethylene, and the α-olefin having 6 to 8 carbon atoms. It is more preferable to prepolymerize with ethylene.

  The polymerization temperature is usually lower than the temperature at which the ethylene-α-olefin copolymer melts, preferably 0 to 150 ° C, more preferably 30 to 100 ° C, and even more preferably 50 to 90 ° C. is there. From the viewpoint of expanding the molecular weight distribution (Mw / Mn) of the ethylene-α-olefin copolymer, a higher polymerization temperature is preferable.

  The polymerization time is usually 1 to 20 hours (as an average residence time in the case of a continuous polymerization reaction). From the viewpoint of expanding the molecular weight distribution (Mw / Mn) of the ethylene-α-olefin copolymer, it is preferable that the polymerization time (average residence time) is long.

  Further, for the purpose of adjusting the melt fluidity of the copolymer, hydrogen may be added to the polymerization reaction gas as a molecular weight regulator, and an inert gas may be allowed to coexist in the polymerization reaction gas. The molar concentration of hydrogen in the polymerization reaction gas with respect to the molar concentration of ethylene in the polymerization reaction gas is usually 0.1 to 3 mol% as the molar concentration of ethylene in the polymerization reaction gas is 100 mol%. Moreover, from the viewpoint of widening the molecular weight distribution (Mw / Mn) of the ethylene-α-olefin copolymer, it is preferable that the molar concentration of hydrogen in the polymerization reaction gas is high.

  The component (B) ethylene-α-olefin copolymer is an ethylene-α-olefin copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms, and the flow activation. It is an ethylene-α-olefin copolymer having an energy (Ea) of less than 40 kJ / mol. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4 -Methyl-1-pentene, 4-methyl-1-hexene and the like can be mentioned, and 1-butene, 1-hexene and 1-octene are preferable. Moreover, said C3-C20 alpha olefin may be used independently and may use 2 or more types together.

  Examples of the ethylene-α-olefin copolymer used in the component (B) include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer. Polymer, etc., preferably ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-butene-1-hexene copolymer, ethylene -1-butene-1-octene copolymer.

  The melt flow rate (MFR) of the ethylene-α-olefin copolymer of component (B) is usually 0.01 to 100 g / 10 min. The MFR is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more, from the viewpoint of reducing the load on the extruder during molding. Further, the MFR is preferably 10 g / 10 min or less from the viewpoint of improving calendar workability and mechanical strength. In addition, this MFR is measured on condition of temperature 190 degreeC and load 21.18N in the method prescribed | regulated to JISK7210-1995.

The density of the ethylene-α-olefin copolymer of component (B) is usually 870 to 960 kg / m ³ . The density is preferably 930 kg / m ³ or less, more preferably 925 kg / m ³ or less, and still more preferably 920 kg / m ³ or less, from the viewpoint of enhancing mechanical strength and flexibility. Moreover, from a viewpoint of improving heat resistance, it is 880 kg / m < ³ > or more, More preferably, it is 890 kg / m < ³ > or more. The density is measured according to a method defined in JIS K7112-1980.

  The melt flow rate ratio (MFRR) of the ethylene-α-olefin copolymer of component (B) is usually 10-200. The MFRR is preferably 15 or more from the viewpoint of improving calendar processability. Moreover, from a viewpoint of raising mechanical strength, Preferably it is 100 or less, More preferably, it is 50 or less. The MFRR is a melt flow rate (MFR-H, unit: g / 10 minutes) measured under the conditions of a test load of 211.83 N and a measurement temperature of 190 ° C. in the method defined in JIS K7210-1995. In the method defined in JIS K7210-1995, it is a value divided by the melt flow rate (MFR) measured under conditions of a load of 21.18 N and a temperature of 190 ° C.

  Component (B) ethylene-α-olefin copolymer is produced by using a known polymerization catalyst such as a Ziegler-Natta catalyst, a chromium catalyst, a metallocene catalyst, a liquid phase polymerization method, or a slurry polymerization method. And a production method by a known polymerization method such as a gas phase polymerization method or a high pressure ion polymerization method. The polymerization method may be either a batch polymerization method or a continuous polymerization method, and may be a multistage polymerization method having two or more stages.

Examples of the Ziegler-Natta catalyst include the following catalysts (1) or (2).
(1) A catalyst comprising a component in which at least one selected from the group consisting of titanium trichloride, vanadium trichloride, titanium tetrachloride and titanium haloalcolate is supported on a magnesium compound carrier, and an organometallic compound as a cocatalyst ( 2) A catalyst comprising an organometallic compound which is a coprecipitate of a magnesium compound and a titanium compound or a eutectic and a cocatalyst.

  Examples of the chromium-based catalyst include a catalyst comprising a component in which a chromium compound is supported on silica or silica-alumina, and an organometallic compound as a cocatalyst.

Examples of the metallocene catalyst include the following catalysts (1) to (4).
(1) A catalyst comprising a transition metal compound having a group having a cyclopentadiene skeleton and a component containing an alumoxane compound. (2) A component containing the transition metal compound, and ionic properties such as trityl borate and anilinium borate. catalyst comprising component containing a compound (3) said transition metal compound and component comprising a component containing an ionic compound, a catalyst (4) SiO ₂ the components of the consisting of components including an organic aluminum compound, Al ₂ Catalyst obtained by supporting or impregnating an inorganic particulate carrier such as O ₃ or a particulate polymer carrier such as an olefin polymer such as ethylene or styrene.

  Examples of the flame retardant for component (C) include metal hydroxides, metal oxides, inorganic salts / inorganic hydrated compounds, silane compounds, phosphorus compounds, bromine compounds, and chlorine compounds.

  Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, zirconium hydroxide, hydrotalcite and the like.

  Examples of the metal oxide include antimony pentoxide, antimony trioxide, zinc oxide, ferrocene, copper oxide, calcium oxide, nickel oxide, bismuth oxide, zinc stannate, calcium aluminate, and the like.

  Examples of the inorganic salt / inorganic hydrated compound include calcium carbonate, barium metaborate, kaolin clay, wax stone clay, dosonite, calcium aluminate silicate, and the like.

  Examples of the silane compound include silicon oil, silicon gum, and the like, and those having a functional group introduced thereto.

  Examples of the phosphorus compound include triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate as the non-halogen phosphate, and examples of the halogen-containing phosphate include trichloroethyl phosphate, Tris dichloropropyl phosphate, tris β-chloropropyl phosphate, etc., and other phosphorus compounds include polyphosphate ammonium, polyphosphate amide, polychlorophosphate, condensed phosphonate, aromatic condensed phosphate, red phosphorus Etc.

  Examples of the bromine-based compound include decabromodiphenyl oxide, hexabromochlorodecane, ethylenebistetrabromophthalimide, hexapromobenzene, and the like.

  Examples of the chlorinated compound include perchlorocyclopentadecane, chlorinated paraffin, chlorinated polyolefin, and chlorinated polyethylene.

  As a flame retardant of a component (C), you may use individually or in combination.

  As the flame retardant of component (C), non-halogen and non-phosphorus flame retardants are preferred, metal hydroxides, metal oxides, inorganic salts / inorganic hydrated compounds are more preferred, and metal hydroxides are more preferred. Aluminum hydroxide and magnesium hydroxide are particularly preferred.

  The content of component (A) and component (B) in the resin composition of the present invention is such that the total amount of component (A) and component (B) is 100% by weight, and the content of component (A) is 90 to 40. % By weight, and the content of component (B) is 10 to 60% by weight. If the content of the component (A) is too small (the content of the component (B) is too large), the calendar workability may be inferior, and the content of the component (A) is too large (the content of the component (B)) If the amount is too small), the mechanical strength and flexibility may be inferior. Preferably, the content of component (A) is 80 to 50% by weight, and the content of component (B) is 20 to 50% by weight.

  Content of the component (C) in the resin composition of this invention is 0.1-200 weight part per 100 weight part of total amounts of a component (A) and a component (B). From the viewpoint of enhancing the flame retardancy of the waterproof sheet, the content is preferably 1% by weight or more, more preferably 10 parts by weight or more, and further preferably 30 parts by weight or more. Moreover, from a viewpoint of improving a softness | flexibility and mechanical strength, Preferably it is 150 weight part or less, More preferably, it is 120 weight part or less.

  If necessary, additives such as an antioxidant, a lubricant, an antistatic agent, a weathering stabilizer, a pigment, and a metal soap for workability improving agent may be added to the resin composition of the present invention.

  The resin composition of the present invention is prepared by, for example, tumbler blender, Henschel mixer by melt kneading component (A), component (B), component (C), and other components as necessary, by a known method. It is obtained by dry blending using a single screw extruder, a multi-screw extruder, or the like, or by melt kneading using a kneader or Banbury mixer. The component (C) and other components may be used for melt-kneading as one or more master batches, and the component (A) and / or the component (B) may be an organosilane compound or an acid as necessary. It may be modified with an anhydride or the like, and the modification may be carried out at the time of melt-kneading the component (A), the component (B), the component (C) and other components added as necessary, with an organosilane compound or an acid. A method of adding a modifier such as an anhydride and a radical generator such as an organic oxide, and in advance, the component (A) and / or the component (B) is melt-kneaded with the modifier and the radical generator. It is done by the method to keep.

  Examples of the method for producing the waterproof sheet of the present invention include a method of calendering a resin composition melt-kneaded by an extruder or a Banbury mixer, a method of T-die casting the resin composition, and the like. The method is preferred.

  As a processing machine used for calendering, a known calendering machine is used, and usually the molten resin composition melt-kneaded by an extruder or a Banbury mixer is transferred to a receiving roll, and then transferred to a supply roll by an appropriate amount. Further, it is transferred to 2 to 6 calender rolls, and is gradually spread into a sheet shape, and is composed of an apparatus that can be wound up through a take-out roll or a cooling / stretching roll. The calender roll includes 4 to 6 reverse L-type, horizontal type, Z-type, and composite type, and the roll temperature is usually 120 to 180 ° C. although it depends on the melting point of the resin composition to be used.

  In the manufacture of the waterproof sheet, a reinforcing material may be used and a sheet having the reinforcing material may be used. The sheet thickness is usually 0.1 to 10 mm.

  The waterproof sheet of the present invention is, for example, a waterproof enforcement sheet for civil engineering widely used outdoors; industrial waste landfills, agricultural ponds, golf courses and other ponds used for the purpose of preventing water and sewage from penetrating underground It is used for roofing waterproof sheets for houses, parking lots, buildings, etc .;

Hereinafter, the present invention will be described with reference to examples and comparative examples.
The physical properties in Examples and Comparative Examples were measured according to the following methods.

(1) Melt flow rate (MFR, unit: g / 10 minutes)
In the method defined in JIS K7210-1995, the measurement was performed under the conditions of a load of 21.18 N and a temperature of 190 ° C.

(2) Melt flow rate ratio (MFRR)
In the method specified in JIS K7210-1995, the melt flow rate (MFR-H, unit: g / 10 minutes) measured under conditions of a test load of 211.83 N and a measurement temperature of 190 ° C. is specified in JIS K7210-1995. In this method, the value divided by the melt flow rate (MFR) measured under the conditions of a load of 21.18 N and a temperature of 190 ° C. was defined as MFRR.

(3) Density (Unit: kg / m ³ )
The density was measured according to the method defined in JIS K7112-1980.

(4) Molecular weight distribution (Mw / Mn)
The measurement was performed under the following conditions (1) to (7) using a gel permeation chromatograph (GPC) method. The weight average molecular weight (Mw) in terms of polystyrene and the number average in terms of polystyrene using a calibration curve prepared in advance using a standard polystyrene (TSK STANDARD POLYSTYRNE manufactured by Tosoh Corporation) with a narrow molecular weight distribution that can be regarded as monodisperse. The molecular weight (Mn) was determined, and the molecular weight distribution (Mw / Mn) was determined from them.
(1) Equipment: Waters 150C manufactured by Water
(2) Separation column: TOSOH TSKgelGMH-HT
(3) Measurement temperature: 145 ° C
(4) Carrier: Orthodichlorobenzene
(5) Flow rate: 1.0 mL / min
(6) Injection volume: 500 μL
(7) Detector: Differential refraction

(5) Flow activation energy (Ea, unit: kJ / mol)
Using a viscoelasticity measuring device (Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), a melt complex viscosity-angular frequency curve at 130 ° C., 150 ° C., 170 ° C. and 190 ° C. was measured under the following measurement conditions. From the obtained melt complex viscosity-angular frequency curve, calculation software Rhios V. The activation energy (Ea) was determined using 4.4.4.
<Measurement conditions>
Geometry: Parallel plate Plate diameter: 25mm
Plate spacing: 1.2-2mm
Strain: 5%
Angular frequency: 0.1 to 100 rad / sec Measurement atmosphere: Under nitrogen

(6) Melt complex viscosity (η ^* , unit: Pa · sec)
The melt complex viscosity at 190 ° C. at an angular frequency of 100 rad / sec was determined from the measurement result of the melt complex viscosity at 190 ° C.-angular frequency obtained when the above-mentioned (5) flow activation energy was measured.

(7) Melt tension (MT, unit: cN)
Using a melt tension tester manufactured by Toyo Seiki Seisakusho, a molten resin filled in a 9.5 mmφ barrel at a temperature of 190 ° C., a piston descending speed of 5.5 mm / min, a diameter of 2.09 mmφ, and a length of 8 mm The melted resin extruded from the orifice was wound up at a winding speed of 40 rpm / min using a winding roll having a diameter of 150 mmφ, and the tension value immediately before the molten resin broke was measured. It shows that melt tension is so large that this value is large.

(8) Intrinsic viscosity ([η], unit: dl / g)
A tetralin solution (hereinafter, referred to as a blank solution) in which 2,6-di-t-butyl-p-cresol (BHT) is dissolved at 0.5 g / L, and an ethylene polymer resin of the blank solution is used. A 135 ° C. tetralin solution (hereinafter referred to as a sample solution) having a concentration of 1 mg / ml was prepared, and the falling time of the blank solution and the sample solution at 135 ° C. was measured with an Ubbelohde viscometer, After calculating the relative viscosity (η _rel ) at 135 ° C. from the falling time, it was calculated from the following formula.
[Η] = 23.3 × log (η _rel )

(9) Oxygen index (unit:%)
The oxygen index was measured according to JIS K7201-1976. The larger this value, the better the flame retardancy.

(10) Tensile test A press sheet having a thickness of 2 mm was prepared and punched from the sheet into a No. 3 dumbbell mold described in JIS K6251-1993. The distance between marked lines was 20 mm, the distance between chucks was 60 mm, and the tensile speed was A tensile test was performed under the condition of 500 mm / min, and the tensile fracture strength (unit: MPa) and the tensile fracture elongation (unit:%) were determined. The larger these values, the better the mechanical strength.

(11) Vicat softening temperature (VST)
In the method defined in JIS K7206-1991, measurement was performed under the conditions of a test load of 9.8 N and a heating rate of 50 ° C./hr, and the temperature when the needle entered 1 mm into the test piece was obtained. The higher the temperature, the better the heat resistance.

(12) Flexural rigidity Measured according to ASTM D747. The lower this value, the better the flexibility.

(13) Calendar workability Using a roll having a diameter of 8 inches (calendar roll), under conditions of a roll surface temperature of 140 ° C., a roll speed of 11.5 m / min (speed ratio of 1: 1.5), and a roll interval of 0.5 mm, After 150 g of the sample was wound for 5 minutes, the molten sheet was taken out and cooled to prepare a sheet. The roll-off property and take-off property when taking out the molten sheet were evaluated as follows.
<Releasing property>
○: The molten sheet and the roll do not stick.
X: The molten sheet and the roll stick.
<Catchability>
○: The molten sheet peeled off from the roll does not drip.
X: The molten sheet peeled off from the roll drips.

Example 1
(1) Preparation of cocatalyst carrier Silica (Sypolol 948 manufactured by Devison, average particle size = 55 μm; pore volume = 1.67 ml) heat-treated at 300 ° C. under nitrogen flow in a reactor equipped with a nitrogen-substituted stirrer / G; specific surface area = 325 m ² / g) 2.8 kg and 24 kg of toluene were added and stirred. After cooling to 5 ° C., 0.91 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.43 kg of toluene were added dropwise over 33 minutes while maintaining the reactor temperature at 5 ° C. . After completion of the dropping, the mixture was stirred at 5 ° C. for 1 hour and then at 95 ° C. for 3 hours and filtered. The obtained solid product was washed 6 times with 21 kg of toluene. Thereafter, 6.9 kg of toluene was added to form a slurry, which was allowed to stand overnight.

To the slurry obtained above, 2.05 kg of diethyl zinc in hexane (diethyl zinc concentration: 50 wt%) and 1.3 kg of hexane were added and stirred. Thereafter, after cooling to 5 ° C., a mixed solution of 0.77 kg of pentafluorophenol and 1.17 kg of toluene was added dropwise over 61 minutes while keeping the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, 0.11 kg of H ₂ O was added dropwise over 1.5 hours while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1.5 hours and at 55 ° C. for 2 hours. Thereafter, 1.4 kg of diethylzinc in hexane (diethylzinc concentration: 50 wt%) and 0.8 kg of hexane were added at room temperature. After cooling to 5 ° C., a mixed solution of 0.44 kg of 3,4,5-trifluorophenol and 0.77 kg of toluene was added dropwise over 60 minutes while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, 0.077 kg of H ₂ O was added dropwise over 1.5 hours while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C for 1.5 hours, at 40 ° C for 2 hours, and further at 80 ° C for 2 hours. Stirring was stopped, the supernatant liquid was extracted to a remaining amount of 16 L, 11.6 kg of toluene was added, and the mixture was stirred. The temperature was raised to 95 ° C. and stirred for 4 hours. The solid component was allowed to settle, and when the interface between the precipitated solid component layer and the upper slurry portion was seen, the upper slurry portion was removed, and then the remaining liquid component was filtered through a filter. The obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Thereafter, by drying, a solid component (hereinafter referred to as promoter support (a-1)) was obtained.

(2) Prepolymerization In an autoclave with a stirrer having an internal volume of 210 liters, which had been previously purged with nitrogen, 0.71 g of the promoter support (a-1), 80 liters of butane, and 0.5 liters as normal temperature and normal pressure hydrogen were charged. Thereafter, the autoclave was raised to 30 ° C. Further, ethylene was charged in an amount of 0.03 MPa at the gas phase pressure in the autoclave, and after the system was stabilized, 208 mmol of triisobutylaluminum and 70 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. While raising the temperature to 50 ° C. and supplying ethylene and hydrogen continuously, prepolymerization was carried out at 50 ° C. for a total of 4 hours. After completion of the polymerization, ethylene, butane, hydrogen gas, and the like were purged, and the remaining solid was vacuum dried at room temperature, so that 13.3 g of ethylene polymer per 1 g of the promoter support (a-1) was prepolymerized. A polymerization catalyst component was obtained.

(3) Continuous gas phase polymerization Using the above prepolymerization catalyst component, ethylene and 1-hexene were copolymerized in a continuous fluidized bed gas phase polymerization apparatus. The polymerization conditions were a temperature of 75 ° C., a total pressure of 2 MPa, a gas linear velocity of 0.28 m / s, a hydrogen molar ratio to ethylene of 0.895%, a 1-hexene molar ratio to ethylene of 1.91%, and a gas composition during the polymerization. In order to maintain a constant, ethylene, 1-hexene and hydrogen were continuously supplied. Furthermore, the pre-polymerization catalyst component and triisobutylaluminum were continuously supplied at a constant ratio so that the total powder weight of the fluidized bed was maintained at 80 kg and the average polymerization time was 3.6 hr. By polymerization, a powder of component (A) (hereinafter referred to as PE-1) which is an ethylene-1-hexene copolymer was obtained with a polymerization efficiency of 22 kg / hr.

(4) Granulation of ethylene-1-hexene copolymer powder The PE-1 powder obtained above was fed with an LCM50 extruder manufactured by Kobe Steel, Ltd., at a feed rate of 50 kg / hr, a screw rotation speed of 450 rpm, and a gate opening of 4. The pellets of PE-1 were obtained by granulation under conditions of 0.2 mm, a suction pressure of 0.2 MPa, and a resin temperature of 200 to 230 ° C. Table 1 shows the physical properties of PE-1 pellets.

  60% by weight of PE-1 pellets, 40% by weight of commercially available linear low density polyethylene (Exelen FX CX3007; hereinafter referred to as PE-2) manufactured by Sumitomo Chemical Co., Ltd., and magnesium hydroxide (trade name, manufactured by Kyowa Chemical Co., Ltd.) Kisuma 5B; hereinafter referred to as “flame retardant K.” 50 parts by weight (with the total amount of PE-1 and PE-2 being 100 parts by weight) using Labo Plast Mill (manufactured by Toyo Seiki Co., Ltd.), set temperature 160 The resin composition was obtained by kneading for 10 minutes under the conditions of ° C and a rotational speed of 60 rpm. Table 2 shows the evaluation results of the physical properties of the obtained resin composition.

Example 2
The same procedure as in Example 1 was conducted except that the amount of flame retardant K was 100 parts by weight (the total amount of PE-1 and PE-2 was 100 parts by weight). Table 2 shows the evaluation results of the physical properties of the obtained resin composition.

Example 3
The procedure was the same as Example 1 except that a commercially available linear low-density polyethylene (Exelen VL VL100; Sumitomo Chemical Co., Ltd .; hereinafter referred to as PE-3) was used instead of PE-2. Table 2 shows the evaluation results of the physical properties of the obtained resin composition.

Comparative Example 1
The same procedure as in Example 1 was performed except that only PE-1 pellets were used. The evaluation results of the physical properties are shown in Table 2.

Comparative Example 2
Using 100% by weight of PE-1 pellets and 100 parts by weight of flame retardant K (with PE-1 as 100 parts by weight), Labo Plast Mill (manufactured by Toyo Seiki Co., Ltd.), set temperature 160 ° C., rotation speed The resin composition was obtained by kneading for 10 minutes under the condition of 60 rpm. Table 2 shows the evaluation results of the physical properties of the obtained resin composition.

Comparative Example 3
100% by weight of PE-2, 50 parts by weight of flame retardant K (with PE-2 as 100 parts by weight), Labo Plast Mill (manufactured by Toyo Seiki Co., Ltd.), set temperature 160 ° C., rotation speed 60 rpm The resin composition was obtained by kneading for 10 minutes under the above conditions. Table 3 shows the evaluation results of the physical properties of the obtained resin composition.

Comparative Example 4
60% by weight of PE-2, 60% by weight of commercially available linear low density polyethylene (Novatech LL UE320; hereinafter referred to as PE-4) manufactured by Nippon Polychem, and 150 parts by weight of flame retardant K (PE- 2 and the total amount of PE-4 as 100 parts by weight) using a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) for 10 minutes under the conditions of a preset temperature of 160 ° C. and a rotational speed of 60 rpm. Obtained. Table 3 shows the evaluation results of the physical properties of the obtained resin composition.

Comparative Example 5
The same procedure as in Comparative Example 3 was performed except that a commercially available linear low density polyethylene (DuPont Dow Elastomers, Engage 8100; hereinafter referred to as PE-5) was used instead of PE-2. Table 3 shows the evaluation results of the physical properties of the obtained resin composition.

Comparative Example 6
It carried out similarly to the comparative example 3 except having replaced with PE-2 and using the commercially available linear low density polyethylene (Affinity PF1140 by Dow Chemical company; hereafter, referred to as PE-6.). Table 3 shows the evaluation results of the physical properties of the obtained resin composition.

Claims (3)

The following components (A), (B) and (C) are contained, the total amount of component (A) and component (B) is 100% by weight, and the content of component (A) is 90 to 40% by weight, Waterproofing wherein the content of the component (B) is 10 to 60% by weight and the content of the component (C) is 0.1 to 200 parts by weight per 100 parts by weight of the total amount of the components (A) and (B) Resin composition for sheet.
(A): The flow activation energy (Ea) is 40 kJ / mol or more, and the melt flow rate (MFR) measured under conditions of a temperature of 190 ° C. and a load of 21.18 N specified in JIS K7210 is 0.1. Ethylene-α-olefin copolymer (B) having a molecular weight distribution (Mw / Mn) of 5 to 25: ethylene having a flow activation energy (Ea) of less than 40 kJ / mol α-olefin copolymer (C): flame retardant containing metal hydroxide A waterproof sheet comprising the resin composition according to claim 1. The manufacturing method of the waterproof sheet which calendar-processes the resin composition of Claim 1.