JP3506538B2 - Polypropylene resin sheet - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin sheet having excellent impact resistance, transparency, rigidity, heat resistance, whitening resistance, etc. More specifically, a propylene polymer and a specific ethylene / α-olefin The present invention relates to a sheet made of a propylene resin composition containing a copolymer, another ethylene polymer, or a nucleating agent.

[0002]

2. Description of the Related Art Polypropylene-based sheets are subjected to secondary processing such as thermoforming, containers for food cups, lids, trays, blister packs, etc., stationery applications such as clear files, holders, confectionery, dolls, etc. Folded products such as clear cases, or PTs for medicines, tablets, etc.
It is widely used for P (press-through pack) containers and also for industrial materials. The performance required for the seat is
The impact resistance, transparency, rigidity, heat resistance, whitening resistance, etc. are generally different, although they differ slightly depending on the application. Conventionally, for applications requiring such properties, a method of mixing an ethylene-propylene copolymer rubber (EPR), polyethylene, ultra-low density polyethylene (VLDPE), etc. with a polypropylene resin (see, for example, JP-A-58-11536, Kaisho 52-7274
4, JP-A-62-174233). However, such a composition has a drawback that the effect of improving impact resistance is not sufficient, and further transparency and heat resistance are lowered. That is, when VLDPE is mixed, these compositions have not been sufficiently and satisfactorily improved in that they have a low melting point, a low heat resistance, a large amount of high branching and low molecular weight components, and a large amount of elution into the contents. It was Also, heat resistance,
There is also a method of mixing linear low-density polyethylene in order to suppress the decrease of the eluted components, but there is a drawback that the transparency is decreased.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polypropylene resin sheet having excellent impact resistance and transparency in order to meet these requirements, and in particular from the viewpoint of hygiene. A polypropylene-based resin sheet that has good transparency so that you can see the objects, has a small amount of resin elution components so that the resin components do not migrate to the contents, has heat resistance to withstand sterilization, and has excellent impact resistance. Providing the food sheet cup, tray,
It is used as a lid, a file for stationery, a binder, and a sheet for daily sundries, industrial materials, medical care, etc.

[0004]

Means for Solving the Problems As a result of intensive studies made by the present inventors in view of the above objects, the ethylene / α having a narrow specific molecular weight distribution and a narrow composition distribution in a propylene-based polymer.
A polypropylene resin sheet excellent in impact resistance while maintaining transparency and heat resistance by blending an olefin copolymer or an ethylene polymer if necessary with a nucleating agent, which is a food cup, tray or lid. , Or stationery files, binders, daily miscellaneous goods, industrial materials,
The present invention has been accomplished by finding that a sheet used for medical purposes can be obtained.

That is, the present invention is, firstly, the periodic table I containing (A) a propylene-based polymer in an amount of 95 to 50% by weight and (B) (a) a ligand having a cyclopentadienyl skeleton.
It is obtained by (co) polymerizing ethylene or ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst containing a Group V transition metal compound as an essential component.
(B) With a density of 0.86 to 0.97 g / cm ³ , (c) a melt flow rate of 0.01 to 50 g / 10 minutes, (d)
The molecular weight distribution (Mw / Mn) is 1.8 to 3.5,
(E) 5 to 50% by weight of an ethylene (co) polymer (B) having a composition distribution (Cb) of 1.2 or less, and (C) other
Ethylene polymer 10 to 35% by weight (however, A + B +
C total 100% by weight).
The polypropylene-based resin sheet is characterized in that

Secondly, the present invention relates to (A) polypropylene
95-50% by weight of polymer, (B) (a) cyclopenta
Group IV of the periodic table containing a ligand having a dienyl skeleton
In the presence of a catalyst containing a transition metal compound as an essential component,
Ethylene or ethylene and α-olefin having 3 to 20 carbon atoms
(B) Dense obtained by (co) polymerizing
(Ha) melt flow at a rate of 0.86 to 0.97 g / cm ^3.
-Rate of 0.01 to 50 g / 10 minutes, (d) molecular weight
Cloth (Mw / Mn) is 1.8 to 3.5, and (e) composition
Ethylene (co) polymer having a cloth (Cb) of 1.2 or less
(B) 5 to 50% by weight, or (A), (B) and
(C) Up to 45% by weight of another ethylene polymer (however,
Resin component 10 consisting of 100% by weight of A + B + C)
0 parts by weight of (D) talc, metal organic carboxylate
Salts, aromatic phosphate compounds and sorbitol
0.01 to at least one selected from the group of compounds
The polypropylene resin sheet is characterized in that 2 parts by weight are blended .

The present invention will be described in detail below. The (A) propylene-based polymer that forms the composition of the present invention is a propylene homopolymer, a block copolymer of propylene and another α-olefin, or a random copolymer of propylene and another α-olefin. Etc., especially propylene / α-
A random copolymer with an olefin and a mixture of a propylene homopolymer and a propylene / α-olefin random copolymer are preferable. The propylene / α-olefin copolymer means propylene and 2 to 8 carbon atoms (however, 3 carbon atoms).
A) and one or more kinds of α-olefins), particularly preferably propylene / ethylene random copolymer, propylene / ethylene / butene-1 random copolymer, propylene / butene-1. It is a random copolymer. The propylene-based polymer is polymerized by a known technique using a Ziegler-Natta type catalyst.

The α-olefin content in the propylene / α-olefin copolymer is preferably 1 to 20% by weight, respectively. When the content of α-olefin is less than 1% by weight, the impact strength is not sufficient. Further, if the content of α-olefin exceeds 20% by weight, the rigidity is low and there is a possibility that it is not suitable as a sheet or the like.

The melt flow rate (MFR) of the (A) propylene polymer of the present invention is 0.1 to 30 g / 10 mi.
n, more preferably 0.3 to 20 g / 10 min. If the MFR is less than 0.1 g / 10 min, the fluidity is poor and molding becomes difficult. Also 30g / 1
If it exceeds 0 min, the impact strength is weak and the sheet is unsuitable. These MFRs may be prepared by thermally decomposing a polymerized polymer together with an organic peroxide.

The (B) ethylene (co) polymer of the present invention means a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, and optionally a cocatalyst and an organoaluminum compound. Ethylene or ethylene and a carbon number of 3 to 3 in the presence of a catalyst containing a carrier.
It is obtained by polymerizing or copolymerizing with 20 α-olefins. Further, the catalyst obtained by preliminarily polymerizing ethylene and / or the α-olefin with the above catalyst may be used as the catalyst.

The above α-olefin has 3 to 10 carbon atoms.
20, preferably 3 to 12, specifically, propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1,
And so on. The content of these α-olefins is usually selected in the range of 30 mol% or less, preferably 3 to 20 mol%.

Cyclopenta, a transition metal compound of Group IV of the periodic table, containing (a) a ligand having a cyclopentadienyl skeleton, which is a catalyst for producing the above-mentioned (B) ethylene (co) polymer of the present invention The dienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group or the like. The substituted cyclopentadienyl group includes a hydrocarbon group having 3 to 10 carbon atoms, a silyl group, a silyl-substituted alkyl group, a silyl-substituted aryl group, a cyano group, a cyanoalkyl group, a cyanoaryl group, a halogen group, a haloalkyl group, and a halosilyl group. And a substituted cyclopentadienyl group having at least one kind of substituent selected from the group. The substituted cyclopentadienyl group may have two or more substituents, and the substituents may be bonded to each other to form a ring.

Examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group and isopropyl. Group, n-butyl group,
Alkyl groups such as isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group; cycloalkyl groups such as cyclopentyl group, cycloalkyl group; phenyl group, tolyl group Examples thereof include aryl groups such as groups; and aralkyl groups such as benzyl groups and neophyl groups. Of these, alkyl groups are preferred.

Preferred examples of the substituted cyclopentadienyl group include methylcyclopentadienyl group, ethylcyclopentadienyl group, n-hexylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
3-n-butylmethylcyclopentadienyl group, 1,3
Specific examples thereof include an -n-propylmethylethylcyclopentadienyl group. Among these, the substituted cyclopentadienyl group of the present invention is preferably a cyclopentadienyl group substituted with an alkyl group having 3 or more carbon atoms,
A 1,3-substituted cyclopentadienyl group is particularly preferable.

The substituted cyclopentadienyl group in the case where the substituents, ie, the hydrocarbons, are bonded to each other to form one or two or more rings, an indenyl group and a carbon number of 1 are used.
A substituted indenyl group, a naphthyl group, and a carbon number of 1 to 8 substituted with a substituent such as a hydrocarbon group (eg, an alkyl group) having 8 to 8 carbon atoms.
Preferred are a substituted naphthyl group substituted by a substituent such as a hydrocarbon group (alkyl group) and a substituted fluorenyl group substituted by a substituent such as a hydrocarbon group having 1 to 8 carbon atoms (alkyl group). It is mentioned as a thing.

Examples of the transition metal of the group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton include zirconium, titanium and hafnium, with zirconium being particularly preferred. The transition metal compound usually has 1 to 3 ligands having a cyclopentadienyl skeleton, and when they have 2 or more ligands, they may be bonded to each other by a bridging group. Examples of the cross-linking group include an alkylene group having 1 to 4 carbon atoms, an alkylsilanediyl group, and a silanediyl group. As a ligand other than the ligand having a cyclopentadienyl skeleton in the transition metal compound of Group IV of the periodic table, hydrogen and a hydrocarbon group having 1 to 20 carbon atoms (alkyl group, Alkenyl group, aryl group, alkylaryl group, aralkyl group, polyenyl group, etc.), halogen, metaalkyl group, metaaryl group and the like.

The following are specific examples of the transition metal compound of Group IV of the periodic table containing the above-mentioned ligand having a cyclopentadienyl skeleton. That is, as the monoalkyl metallocene, bis (cyclopentadienyl) titanium methyl chloride, bis (cyclopentadienyl) titanium phenyl chloride, bis (cyclopentadienyl) zirconium methyl chloride, bis (cyclopentadienyl) zirconium phenyl chloride, etc. There is. Bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) as dialkyl metallocene Examples include hafnium dimethyl and bis (cyclopentadienyl) hafnium diphenyl. Trialkyl metallocenes include cyclopentadienyl titanium trimethyl, cyclopentadienyl zirconium triphenyl, cyclopentadienyl zirconium trineopentyl, cyclopentadienyl zirconium trimethyl, cyclopentadienyl hafnium triphenyl, cyclopentadienyl hafnium triphenyl. Examples include neopentyl and cyclopentadienyl hafnium trimethyl. Moreover, pentamethylcyclopentadienyl titanium trichloride, which is monocyclopentadienyl titanocene, pentaethylcyclopentadienyl titanium trichloride, bis (pentamethylcyclopentadienyl) titanium diphenyl and the like can be mentioned.

The substituted bis (cyclopentadienyl) titanium compounds include bis (indenyl) titanium diphenyl or dichloride, bis (methylcyclopentadienyl) titanium diphenyl or halide; dialkyl, trialkyl, tetraalkyl or pentaalkylcyclopenta Examples of the dienyl titanium compound include bis (1,2-dimethylcyclopentadienyl) titanium diphenyl or dichloride, bis (1,2)
-Diethylcyclopentadienyl) titanium diphenyl or dichloride or other dihalide complex; dimethylsilyldicyclopentadienyl titanium diphenyl or dichloride as silicon, amine or carbon linked cyclopentadiene complex, methylenedicyclopentadienyl titanium diphenyl or dichloride , And other dihalide complexes.

As the zirconocene compound, pentamethylcyclopentadienyl zirconium trichloride,
Pentaethylcyclopentadienyl zirconium trichloride, bis (pentamethylcyclopentadienyl)
Zirconium diphenyl; as alkyl-substituted cyclopentadiene, bis (ethylcyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium dimethyl, haloalkyl or dihalide thereof. Complexes; bis (pentamethylcyclopentadienyl) zirconium dimethyl as dialkyl, trialkyl, tetraalkyl or pentaalkylcyclopentadiene, bis (1,2-dimethylcyclopentadienyl) zirconium dimethyl, and their dihalide complexes; silicon As the carbon-linked cyclopentadiene complex, dimethylsilyldicyclopentadienylzirconium dimethyl or dihalide, methylenedicyclopentene Dienyl zirconium dimethyl or dihalide, such as methylene dicyclopentadienyl zirconium dimethyl or dihalide, and the like.

As another example of the transition metal compound of Group IV of the periodic table of the present invention, a ligand having a cyclopentadienyl skeleton represented by the following general formula and other ligands and transition metal atoms are The thing which forms a ring is also mentioned.

[0021]

[Chemical 1]

In the formula, Cp is a ligand having the cyclopentadienyl skeleton, X is hydrogen, halogen, and a carbon number of 1 to 2
0 represents an alkyl group, an arylsilyl group, an aryloxy group, an alkoxy group, an amido group, a silyloxy group, etc., and Y represents —O—, —S—, —NR—, —PR— or O.
A divalent neutral ligand selected from the group consisting of R, SR, NR ₂ , and PR ₂ , Z is SiR ₂ , CR ₂ , SiR ₂ SiR
₂ , CR ₂ CR ₂ , CR = CR, SiR ₂ CR ₂ , BR
₂ represents a divalent group selected from the group consisting of BR. However, R is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group, a silyl group, a halogenated alkyl group, a halogenated aryl group, or Y, Z or 2 from both Y and Z.
The one or more R groups are those that form a fused ring system. M represents a transition metal atom of Group IV of the periodic table.

Other examples of the transition metal compound of Group IV of the periodic table represented by the formula 1 are (t-butylamido) (tetramethylcyclopentadienyl) -1,2-ethanediylzirconium dichloride, ( t-butylamide)
(Tetramethylcyclopentadienyl) -1,2-ethanediyl titanium dichloride, (methylamido) (tetramethylcyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (methylamido) (tetramethylcyclopentadienyl) -1,2-ethanediyl titanium dichloride, (ethylamido) (tetramethylcyclopentadienyl) methylene titanium dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride, (t-
Butyramido) dimethyl (tetramethylcyclopentadienyl) silane zirconium dibenzyl, (benzylamido) dimethyl (tetramethylcyclopentadienyl)
Examples thereof include silane titanium dichloride and (phenylphosphide) dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride.

As the co-catalyst of the present invention, a co-catalyst capable of effectively using the transition metal compound of Group IV of the periodic table as a polymerization catalyst or capable of balancing the ionic charge in the catalytically activated state is used. Examples of specific cocatalysts include benzene-soluble aluminoxanes of organoaluminum oxy compounds, organoaluminum oxy compounds insoluble in benzene, boron compounds, lanthanoid salts such as lanthanum oxide, and tin oxide. Of these, aluminoxane is most preferable.

The catalyst may be used by supporting it on a carrier of an inorganic compound or an organic compound. The carrier is preferably a porous oxide of an inorganic compound or an organic compound, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , T.
iO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂
Etc. or a mixture thereof, and SiO ₂ —Al _{2
O 3, SiO 2 -V 2 O} 5, SiO 2 -TiO 2, Si
_{O 2 -V 2 O 5, SiO} 2 -MgO, SiO 2 -Cr 2
O _{3 and the} like can be mentioned. Among these, SiO ₂ and A
It is preferable that the main component is at least one component selected from the group consisting of l ₂ O ₃ . Further, as the organic compound, either a thermoplastic resin or a thermosetting resin can be used, and specifically, particulate polyolefin, polyester, polyamide, polynyl chloride, poly (meth) acrylate, polystyrene, poly Examples include norbornene, various natural polymers, and mixtures thereof.

As the organoaluminum compound of the present invention,
Trialkyl aluminums such as triethyl aluminum and triisopropyl aluminum; dialkyl aluminum halides; alkyl aluminum sesquihalides;
Alkyl aluminum dihalide; alkyl aluminum hydride, organic aluminum alkoxide and the like can be mentioned.

The method for producing the ethylene (co) polymer (B) of the present invention is produced by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method or the like in the presence of the above-mentioned catalyst, which is substantially free of a solvent, Aliphatic hydrocarbons such as butane, pentane, hexane, heptane, etc., aromatic hydrocarbons such as benzene, toluene, xylene, etc., alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, etc., in a state where oxygen, water, etc. are substantially cut off. And the like in the presence of an inert hydrocarbon solvent.
The polymerization conditions are not particularly limited, but the polymerization temperature is usually 15 to
The temperature is 350 ° C., preferably 20 to 200 ° C., more preferably 50 to 110 ° C., and the polymerization pressure is usually atmospheric pressure to 70 kg / cm ² G, preferably atmospheric pressure to 20 k in the case of the low and medium pressure method.
g / cm ² G, usually 1500 kg / in the case of the high pressure method
cm ² G or less is desirable. In the case of the low and medium pressure method, the polymerization time is usually 3 minutes to 10 hours, preferably about 5 minutes to 5 hours. In the case of the high pressure method, it is usually 1 minute to 30 minutes, preferably 2 minutes.
Minutes to 20 minutes is desirable. The polymerization is not limited to the one-step polymerization method, and is not particularly limited to a two-step or more multi-step polymerization method in which the polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature and catalyst are different from each other.

Specific (B) of the present invention obtained with the above catalyst
The ethylene (co) polymer has a (b) density of 0.86 to 0.
97 g / cm ³ , preferably 0.89 to 0.95 g / c
It is in the range of m ³ . When the density is less than 0.86 g / cm ³ , the rigidity and heat resistance are poor, and when the density is 0.97 g / cm ³ or more, the impact resistance is insufficient. Moreover, the (C) melt flow rate of the (B) ethylene (co) polymer is 0.01 to 50 g / 10.
Minutes, preferably 0.03 to 30 g / 10 minutes. If the MFR is less than 0.01 g / 10 minutes, the moldability will be poor, and if it is 50 g / 10 minutes or more, the strength will be reduced. Furthermore, the (D) molecular weight distribution parameter (Mw / Mn) of the ethylene (co) polymer (B) is 1.8 to 3.5, preferably 2.0 to 3.0, and more preferably 2.2 to 2.8. Is the range. When Mw / Mn is less than 1.8, the moldability is poor and the impact resistance is 3.5 or more and the impact resistance is poor. When Mw / Mn is in the above range, mechanical strength such as impact strength is remarkably excellent as compared with the conventional ethylene polymer (C). The method for calculating the molecular weight distribution (Mw / Mn) of the (B) ethylene (co) polymer of the present invention is to determine the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC). , This ratio Mw
/ Mn is calculated.

The (e) composition distribution parameter Cb of the ethylene (co) polymer used in the component (B) of the present invention is 1.
It is 2 or less, preferably 1.15 or less, and more preferably 1.1 or less. If it is 1.2 or more, there is a possibility that the effect of remarkably improving the mechanical strength of the ethylene (co) polymer as the component (B) cannot be expected.

The method for measuring the composition distribution parameter of the ethylene (co) polymer used as the component (B) of the present invention is as follows. A heat resistance stabilizer is added to the sample, and the sample is heated and dissolved in ODCB at 135 ° C. to a concentration of 0.2% by weight. The solution is transferred to a column packed with diatomaceous earth (Celite 545) and cooled to 25 ° C at 0.1 ° C / min to deposit a sample on the surface of Celite. Next, while flowing ODCB at a constant flow rate, the column temperature is raised stepwise to 120 ° C. in steps of 5 ° C. to elute the sample and separate the sample. The solution is reprecipitated with methanol, filtered and dried to obtain a sample at each elution temperature. Weight fraction and branching degree of each sample (100 carbon atoms)
The number of branches per 0) is measured. The degree of branching (measured value) is determined by 13 C-NMR.

For the fraction from 30 ° C. to 90 ° C., the branching degree is corrected as follows. That is, the measured branching degree is plotted against the elution temperature, and the correlation is approximated to a straight line by the method of least squares to create a calibration curve. The correlation coefficient of this approximation is sufficiently large. The value obtained from this calibration curve is the branching degree of each fraction. If the elution temperature is 95 ° C. or higher, a linear relationship does not always hold between the elution temperature and the degree of branching, so this correction is not performed.

Next, the weight fraction w _i of each fraction is calculated as the change amount (b) of the branching degree b _i per elution temperature of 5 ° C.
_i- b _i-1 ) to obtain the relative concentration c _i , plot the relative concentration against the branching degree, and obtain a composition distribution curve. This composition distribution curve is divided with a constant width, and the composition distribution parameter Cb is calculated from the following equation.

[0033]

[Equation 1]

Here, C _j and b _j are the relative density and branching degree of the j-th section, respectively. Composition distribution parameter Cb
Is 1 when the composition of the sample is uniform, and the value increases as the composition distribution spreads.

Many proposals have been made for a method of measuring the composition distribution of a polymer. For example, JP-A-60-88016
Then, numerical processing is performed on the assumption that the cumulative weight fraction has a specific distribution (lognormal distribution) with respect to the number of branches of each fractionated sample obtained by solvent fractionating the sample, and the weight average branching degree (Cw)
And the ratio of the number average branching degree (Cn). The accuracy of this approximate calculation is low when the number of branches of the sample and the cumulative weight fraction deviate from the lognormal distribution, and the correlation coefficient R2 is considerably low when the measurement is performed on commercially available LLDPE, and the accuracy of the value is not sufficient. Further, this Cw / Cn measurement method is the same as the Cb of the present invention.
Although it is different from that of Cw /
The value of Cn is considerably larger than Cb.

The specific (B) ethylene (co) polymer of the present invention has a narrow catalyst molecular weight distribution and composition distribution because the active sites of the catalyst are uniform, resulting in excellent impact strength. Also,
Due to the characteristics of this molecular structure, the melting point is low for the density,
Heat fusion is possible at low temperature. These polymers have different properties from the ethylene / α-olefin copolymers of the component (C) obtained by conventional Ziegler type catalysts and Phillips type catalysts (hereinafter collectively referred to as Ziegler type catalysts). .

The ethylene-based polymer (C) component forming the composition of the present invention is roughly classified into two types. The first component (C1) is a Ziegler type catalyst or Phillips catalyst by a conventional ionic polymerization method. Density obtained from (hereinafter collectively referred to as Ziegler type catalyst) 0.86 to 0.97 g / cm
^{3 is} an ethylene polymer or an ethylene / α-olefin copolymer, specifically, high density polyethylene (HD
PE), linear medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), ultra low density polyethylene (VLDPE) and the like.

High density / linear medium / low density polyethylene (HDPE, MDPE, LLDP) using the above Ziegler type catalyst
E) means that the density is in the range of 0.91 to 0.97 g / cm ³ , preferably 0.91 to 0.96 g / cm ³ , and M
FR is 0.05 to 20 g / 10 min, preferably 0.
1 to 10 g / 10 min, more preferably 0.3 to 1
It is selected in the range of 0 g / 5 min. Mw / Mn is not particularly limited, but is generally in the range of 3.0 to 13, preferably 3.5 to 8. The composition distribution is not particularly limited, but it is generally 1.5 or more, preferably 2.0 or more.

The ultra-low density polyethylene (VLDPE) using the Ziegler type catalyst has a density of 0.86 to
Less than 0.91 g / cm ³ , preferably 0.88 to 0.9
05 g / cm ³ , MFR 0.01 to 20 g / 10 mi
n, preferably 0.1 to 10 g / 10 min. The ultra low density polyethylene (VLDPE) is
Linear low density polyethylene (LLDPE) and ethylene
It has a polyethylene having properties intermediate to those of the α-olefin copolymer rubber (EPR, EPDM), and has a maximum peak temperature (T _m ) of 6 by differential scanning calorimetry (DSC).
A specific ethylene / α-olefin copolymer having a property of 0 ° C. or more and a boiling n-hexane insoluble content of 10% by weight or more, which comprises a solid catalyst component containing at least titanium and / or vanadium and an organoaluminum compound. Is a resin that is polymerized using a catalyst that combines the highly crystalline portion of linear low-density polyethylene and the amorphous portion of ethylene / α-olefin copolymer rubber. The strength and heat resistance coexist in a well-balanced manner with the latter characteristics of rubber-like elasticity and low-temperature impact resistance.

Ethylene / α with the above Ziegler type catalyst
-The α-olefin of the olefin copolymer has a carbon number of 3 to 12, preferably 3 to 10, specifically, propylene, butene-1,4-methylpentene-
1, hexene-1, octene-1, decene-1, dodecene-1 and the like. The content of these α-olefins is preferably selected in the range of 3 to 40 mol%.

The second component (C2) of the ethylene-based polymer of the present invention is low density polyethylene (LDPE) produced by high pressure radical polymerization, an ethylene / vinyl ester copolymer,
It is a copolymer with ethylene / α, β-unsaturated carboxylic acid or its derivative.

The above low density polyethylene (LDPE) is
MFR (melt flow rate) of 0.05 to 20g / 1
The range is 0 min, preferably 0.1 to 10 g / 10 min, and more preferably 1.0 to 10 g / 10 min. Within this range, the melt tension of the composition will be in an appropriate range, and sheet formation and the like will be easy. The density is 0.91 ~
0.94 g / cm ³ , preferably 0.912 to 0.93
5 g / cm ³ , more preferably 0.912 to 0.93
It is 0 g / cm ³ . Further, Mw / Mn is 3.0 to 1
2, preferably 4.0 to 8.0.

The ethylene-vinyl ester copolymer of the present invention means vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, stearin produced by a high pressure radical polymerization method and containing ethylene as a main component. It is a copolymer with vinyl ester monomers such as vinyl acrylate and vinyl trifluoroacetate. Of these, vinyl acetate is particularly preferable. That is, a copolymer composed of 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of a vinyl ester, and 0 to 49.5% by weight of another copolymerizable unsaturated monomer is preferable. Particularly, the vinyl ester content is in the range of 3 to 20% by weight, preferably 5 to 15% by weight. The MFR of these copolymers is 0.1 to 20 g / 10 min, preferably 0.3 to 10 g / min.

Typical examples of the copolymer of ethylene of the present invention with α, β-unsaturated carboxylic acid or its derivative include ethylene / (meth) acrylic acid or its alkyl ester copolymer. Examples of these comonomers include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, acrylic acid-n. -Butyl, methacrylic acid-n-
Butyl, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate,
Examples thereof include glycidyl acrylate and glycidyl methacrylate. Among these, alkyl esters of (meth) acrylic acid such as methyl and ethyl are particularly preferable. In particular, the (meth) acrylic acid ester content is in the range of 3 to 20% by weight, preferably 5 to 15% by weight. The MFR of these copolymers is 0.1
-20 g / 10 min, preferably 0.3-10 g / m
in.

The sheet of the present invention comprises the propylene polymer (A) in an amount of 95 to 50% by weight, preferably 93 to 60% by weight, more preferably 87 to 65% by weight,
The (B) ethylene (co) polymer is composed of a resin composition containing 5 to 50% by weight, preferably 7 to 40% by weight, and more preferably 13 to 35% by weight, and (C) the other ethylene-based polymer. It is possible to add up to 45% by weight, preferably up to 35% by weight, more preferably up to 30% by weight. When the ethylene (co) polymer of the component (B) is 5% by weight or less, the modifying effect of the propylene-based polymer is not recognized, and the mechanical properties such as impact strength and the optical properties such as haze are increased. I can't expect. Further, the component (B) is 50% by weight.
If the above is the case, the properties of the propylene-based polymer are deteriorated and the rigidity and the like are deteriorated, which makes it unsuitable for use as a sheet. On the other hand, if the content of (C) is 45% by weight or more, the characteristics of the propylene-based polymer are deteriorated and the rigidity and the like are deteriorated, which makes it unsuitable for use as a sheet.

In order to improve the transparency, rigidity, etc. of the sheet of the present invention, a metal such as a sorbitol compound or an organic carboxylic acid is used.
Salt, aromatic phosphate compound and / or tal
(D) is used.

Examples of the sorbitol compound include dibenzylidene sorbitol, 1,3,2,4-di- (methylbenzylidene) sorbitol, 1,3,2,4- (ethylbenzylidene) sorbitol, 1,3,2,4-. (Methoxybenzylidene) sorbitol, 1,3,2,4-
(Ethoxybenzylidene) sorbitol and the like can be mentioned.

Examples of the metal salt of carboxylic acid include sodium adipate, potassium adipate, aluminum adipate, sodium sebacate, potassium sebacate, aluminum sebacate, sodium benzoate, aluminum benzoate and di-para-t-butyl. Aluminum benzoate, titanium di-para-t-butyl benzoate, chromium di-para-t-butyl benzoate, hydroxy-di-
Examples thereof include t-butyl aluminum benzoate.

The aromatic phosphoric acid ester compound specifically has a structure represented by the following general formulas 2-8.

[0050]

[Chemical 2]

(In the formula, R ₁ and R ₂ represent a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, and M ₁ represents a metal atom of Group I of the periodic table.)

[0052]

[Chemical 3]

(In the formula, R ₃ and R ₄ represent a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, R ₅ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and M ₂ represents a periodic law. In the table, metal atoms of Group I, Group II, and Group III are shown, and a shows the valence of M _2. )

[0054]

[Chemical 4]

(In the formula, R ₆ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₇ and R ₈ each represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group or an aryl group. Or represents an aralkyl group.)

[0056]

[Chemical 5]

[0057]

[Chemical 6]

(In the formula, X represents a direct bond, an alkylene group or an alkylidene group, and R ₉ , R ₁₀ and R
₁₁ R ₁₂ and R ₁₃ each represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. A represents an ammonium ion or an organic ammonium ion, and m and n each represent 1 to 6. )

[0059]

[Chemical 7]

(In the formula, R ₁₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₁₅ and R ₁₆ represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
M ₃ represents a metal atom of Group III or IV of the Periodic Table, Y represents an —OH group when M ₃ is Group III of the Periodic Table, M
_{When 3} is Group IV of the periodic table, OH group and-(OH) ₂
Indicates a group. )

[0061]

[Chemical 8]

(Wherein R ₁₇ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁₈ and R ₁₉ represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, Represents an aralkyl group, and Z is-
OH group or ^-O - shows the _NH ^{4 +} group. )

Typical examples of commercially available aromatic phosphate ester compounds represented by the above formulas 2 to 8 are MARK NA-10, trade name of Asahi Denka Kogyo Co., Ltd.
Examples include MARK NA-11 and MARK NA-21, which may be used alone or in admixture of two or more.

In the present invention, the above-mentioned sorbitol compound, metal salt of organic carboxylic acid, aromatic phosphate ester compound, and talc are used.
Of these, aromatic phosphate compounds are most preferably used because of their low odor.

The amount of these nucleating agents added is such that the resin mixture 10
0.01 to 2 parts by weight, preferably 0.
It is from 03 to 1 part by weight. If the amount is less than 0.01 parts by weight, the transparency is not sufficiently improved, and if the amount is more than 2 parts by weight, the effect is not changed despite the increase in the addition amount, which is uneconomical and has a bad odor.

The polypropylene-based resin sheet in the present invention is not particularly limited, but it is subjected to secondary processing such as thermoforming, for example, food cups, lids, trays, blister packs, containers, clear files, holders, etc. Widely used for stationery applications, folding products such as clear cases such as sweets and dolls, PTP (press through pack) containers such as medicines and tablets, and industrial materials, etc., preferably 0.05 to 5 mm Is 0.1-3m
The thickness is more preferably 0.2 to 2 mm.

In the present invention, not only antioxidants but also lubricants, antistatic agents, antifogging agents, pigments, ultraviolet absorbers, dispersants, etc. may be added, if necessary, as long as the characteristics of the invention are not essentially impaired. Known additives can be added.

[0068]

EXAMPLES AND COMPARATIVE EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, Examples 1 to 7 are references other than the present invention.
This is a practical example. (A), (B), (C) and (D)
The following were used as ingredients.

Component (A): <Propylene-based polymer> A1: Ziegler-catalyzed propylene-ethylene random copolymer (MFR = 1.5 g / 10 minutes, trade name: Nisseki Polypro E
420G Nippon Petrochemical Co., Ltd. A2: Propylene homopolymer with Ziegler catalyst (MFR = 1.8 g / 10 minutes, trade name: Nisseki Polypro E
120G Nippon Petrochemical Co., Ltd. A3: Propylene-ethylene block copolymer with Ziegler catalyst (MFR = 0.5 g / 10 minutes, trade name: Nisseki Polypro E
610G Nippon Petrochemical Co., Ltd.) (B) component: <Ethylene (co) polymer> (B1) Polymerization of ethylene-butene-1 copolymer A stainless steel autoclave with a capacity of 3 L equipped with a stirrer was replaced with nitrogen 1 0.5 L of purified toluene was added. Next, 10 g of butene-1 was added, and bis (n-butylcyclopentadienyl) zirconium dichloride (Z
0.02 mmol as r) methylalumoxane [MA
O] (MAO / Zr = 500 [molar ratio]) was added, and then the temperature was raised to 80 ° C. Next, ethylene was supplied to continuously polymerize while maintaining the pressure at a constant pressure. The resulting ethylene / butene-1 copolymer (B1
The physical properties of -1) were as follows. MFR: 1.9 g / 10 min Density: 0.9238 g / cm ³ Melting point: 116 ° C. Molecular weight distribution (Mw / Mn): 2.1 Composition distribution: 1.03 Similarly, MFR, density, molecular weight distribution, composition distribution Of ethylene copolymers B1-2 different from each other were obtained. The physical properties are shown in Table 1.

(B2) Polymerization of ethylene / octene-1 copolymer A 3 L stainless steel autoclave equipped with a stirrer was replaced with nitrogen, and 1.5 L of purified toluene was added. Next, 150 ml of octene-1 was added and heated to 140 ° C. Next, ethylene was added to 30 kg / cm ² G and then dissolved in toluene (tert-butylamido) dimethyl (tetramethylcyclopentadienyl) silane zirconium dichloride (0.02 m as Zr).
Mol) methylalumoxane [MAO] (MAO / Zr =
After adding the mixed solution of 500 [molar ratio], it heated up at 80 degreeC. Next, ethylene was supplied to carry out the polymerization while continuously maintaining the pressure at a constant pressure. The physical properties of the obtained ethylene / butene-1 copolymer (B2) were as follows. MFR: 2.1 g / 10 min Density: 0.9258 g / cm ³ Melting point: 109 ° C. Molecular weight distribution (Mw / Mn): 2.5 Composition distribution: 1.08

Component (C): <Other ethylene polymer> C1-1: linear low density polyethylene with a Ziegler catalyst (density = 0.925 g / cm ³ , MFR = 0.9 g / 1
0 minutes, trade name: Nisseki Linirex BF2380 manufactured by Nippon Petrochemical Co., Ltd. C1-2: Ultra-low density polyethylene (density = 0.900 g / cm ³ , MFR = 0.5 g / 1)
0 minutes, trade name: Nisseki Softlex D9005 manufactured by Nippon Petrochemical Co., Ltd. C2-1: Low-density polyethylene by high-pressure radical polymerization (density = 0.922 g / cm ³ , MFR = 0.25 g /
10 minutes, trade name: Nisseki Lexron F102, manufactured by Nippon Petrochemical Co., Ltd.

Component (D): <Nucleating agent> Aromatic phosphoric acid ester compound D1: Asahi Denka Co., Ltd. MARK NA-11 D2: Asahi Denka Co., Ltd. MARK NA-10 D3: Asahi Denka Co., Ltd. MARK NA -21 Sorbitol compound D4: Shin Nippon Rika Co., Ltd. Gelol MD Carboxylic acid metal salt D5: Shell Chemical Co., Ltd. A1-PTBBA Inorganic compound D6: Talc Hayashi Kasei Co., Ltd. Micro White 500
0S (average particle size 2μm)

The resin properties and sheet performance were evaluated by the following test methods. Density: Conforms to JIS K6760 MFR: Polypropylene polymer JIS K6758,
Ethylene polymer JIS K6760 compliant Mw / Mn: GPC Waters 150 type Solvent ODC
B135 ° C. Bending stiffness: conforming to JIS K7106 DuPont impact: thickness 1 mm, diameter 50 mm test piece, Toyo Seiki Co., Ltd. Deupon impact tester Izod impact: conforming to JIS K6758 Haze: Direct reading haze meter (suga test according to JIS K7105) Machine HGH-2DP type)

[Examples 1 to 14, Comparative Examples 1 to 7] The components (A), (B), (C) and (D) described above are shown in Tables 1 to 1.
Each composition was prepared by mixing with a general-purpose stirrer in the blending amount shown in Table 3. Each composition was formed into a sheet under the following conditions. <Sheet molding> Extruder: 50 mm screw, T-die width: 500 mm, lip: 0.5 mm Resin temperature: 230 ° C Speed: 2.5 m / min Cooling: polishing method Sheet specifications: width 430 mm, thickness 0.4 mm (total haze) For measurement) 0.1 mm (for DuPont impact and bending stiffness measurement) <Hot press sheet molding> 230 ° C. Thickness 6.0 mm (for Izod impact measurement) The performance of each sheet was measured by the above evaluation method. The results are shown in Tables 1 to 3.

[0075]

The polypropylene resin sheet of the present invention has the following features. The mechanical strength such as impact strength is remarkably higher than that of the conventional polypropylene-based resin sheet, and the sheet made of polypropylene homopolymer or propylene / ethylene random copolymer has excellent optical characteristics and excellent transparency.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08K 5/527 C08K 5/527 // (C08L 23/10 C08L 23:04 23:04) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/00-23/36 C08K 3/00-13/08 C08J 5/18

Claims (6)

(57) [Claims] 1. A transition metal compound of Group IV of the periodic table containing (A) a propylene-based polymer in an amount of 95 to 50% by weight and (B) (a) a ligand having a cyclopentadienyl skeleton as an essential component. (B) Density 0.86 to 0.97 obtained by (co) polymerizing ethylene or ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst containing
(c) Melt flow rate is 0.01 to g / cm ^3.
50 g / 10 minutes, (d) molecular weight distribution (Mw / Mn) 1.
5 to 50% by weight of an ethylene (co) polymer (B) having a composition distribution (Cb) of 1.2 or less.
And (C) other ethylene-based polymer 10 to 35% by weight
(However, the total of A + B + C is 100% by weight)
A polypropylene-based resin sheet , characterized in that it is composed of a product . 2. A polypropylene polymer (A) 95 to 5
0% by weight, having (B) (a) cyclopentadienyl skeleton
A transition metal compound of Group IV of the periodic table containing a ligand
Ethylene or ethylene in the presence of a catalyst containing as an essential component
(Co) polymerization of len and α-olefin having 3 to 20 carbon atoms
(B) Density of 0.86 to 0.
(C) Melt flow rate is 0.0 at 97 g / cm ^3.
1 to 50 g / 10 minutes, (d) molecular weight distribution (Mw / Mn)
1.8 to 3.5, and (e) composition distribution (Cb) is 1.
5 to 50 weight of ethylene (co) polymer (B) having 2 or less
%, Or the other ethylene of (A), (B) and (C)
Up to 45% by weight of polymer (however, the total of A + B + C is 1
To 100 parts by weight of the resin component consisting of
(D) Talc, organic carboxylic acid metal salt, aromatic phosphoric acid
Select from steal compound and sorbitol compound
0.01 to 2 parts by weight of at least one selected is compounded.
The polypropylene-based resin sheet according to claim 1, wherein 3. The propylene-based polymer (A) is a pro-polymer.
Pyrene homopolymer, propylene-ethylene random copolymer
The polypropylene-based resin sheet according to claim 1 or 2, which is a united product or a mixture thereof . Wherein said (A) propylene-based polymer, pro
Characterized by being a pyrene-ethylene block copolymer
Polypropylene resin sheet according to any one of claims 1 to 3. 5. The other ethylene polymer (C) is
At least one selected from the above ethylene (co) polymers
The polypropylene-based resin sheet according to any one of claims 1 to 4, which is a seed . ( C1) Density with Ziegler type catalyst 0.86 to 0.9
7 g / cm ³ Ethylene homopolymer or ethylene / α
-Olefin copolymer (C2) low-density polyethylene by high-pressure radical polymerization,
With ethylene / vinyl ester copolymer or ethylene
Copolymerization with α, β-unsaturated carboxylic acids or their derivatives
Coalescing 6. The (D) is an aromatic phosphate ester type
It is a compound, The polypropylene-type resin sheet of any one of Claims 1-5.