JPH0931265A - Polypropylene resin sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a sheet having a small amount of eluted components of resin components, such heat resistance as to withstand sterilization, excellent in impact resistance and transparency. SOLUTION: This polypropylene-based resin sheet comprises (A) 95-50wt.% of a polypropylene-based polymer and (B) 5-50wt.% of an ethylene (co)polymer satisfying the following (a) to (d) [(a) 0.86-0.97g/cm<3> density, (b) 0.01-50g/10 minutes melt flow rate(MFR), (c) 1.5-4.5 (Mw/Mn) molecular weight distribution and (d) <=2.00 composition distribution parameter Cb].

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, and excellent workability. Combined (A), despite having a narrow molecular weight distribution, it has a relatively broad composition distribution and a low content of low molecular weight components and amorphous components.
A sheet or a composition comprising a resin composition containing a specific ethylene / α-olefin copolymer (B) excellent in mechanical properties, moldability and heat resistance and optionally other ethylene polymer (C) (D) A sheet made of a resin composition containing a nucleating agent.

[0002]

2. Description of the Related Art Polypropylene resin sheets are subjected to secondary processing such as thermoforming, and are used for food cups, lids, trays, blister packs or other containers, or clear files,
It is widely used for stationery applications such as holders, folding products such as clear cases for confectionery and dolls, PTP (press through pack) containers for medicines, tablets, and industrial materials. The performance required for the sheet is slightly different depending on the application, but in general, impact resistance, transparency,
Rigidity, heat resistance, whitening resistance, etc. Conventionally, for applications requiring such properties, a method of mixing a polypropylene resin with ethylene-propylene copolymer rubber (EPR), polyethylene, ultra-low density polyethylene (VLDPE), etc. (for example, JP-A-58-11536, JP-A-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 elution component, but there are drawbacks such as a decrease in transparency, and the effect of improving impact strength etc. is not yet sufficient. In recent years, a high-strength ethylene (co) polymer having a very narrow molecular weight distribution and compositional distribution by a metallocene catalyst has been developed. However, these metallocene-based ethylene (co) polymers have a very narrow composition distribution, and thus the viscosity and the strength change with temperature very rapidly, and generally the process window at the time of molding is narrow. By mixing such an ethylene (co) polymer with a metallocene-based catalyst into a propylene-based resin, the impact strength is considerably improved, but the moldability may be poor.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polypropylene resin sheet which satisfies these requirements and is excellent in impact resistance and transparency. The other purpose is
The transparency is good so that the contents can be checked from the viewpoint of hygiene, etc., the resin elution components are small so that the resin components do not transfer to the contents, the heat resistance is enough to withstand sterilization, and the impact resistance is also high. To provide excellent seats. The sheet is also excellent in moldability during sheet forming, and is used for food cups, trays, lids, stationery files,
It is used as a binder, and also as a sheet for daily sundries, industrial materials, and medical products.

[0004]

Means for Solving the Problems As a result of intensive studies in view of the above-mentioned objects, the present inventors have found that a propylene-based polymer has a narrow molecular weight distribution but a specific ethylene (copolymer) having a relatively wide composition distribution. ) By blending a polymer and, if necessary, another ethylene polymer, and further a nucleating agent, the sheet forming processability is good, and the obtained sheet has excellent impact resistance while maintaining transparency and heat resistance. The present invention has been found to be optimally used for food cups, trays, lids, stationery files, binders, and sheets for daily sundries, industrial materials, medical products, etc.

That is, the first aspect of the present invention is: (A) Propylene polymer 95 to 50% by weight (B) Ethylene (co) polymer 5 to 50% by weight (B) satisfying the following (A) to (D): A) Density 0.86 to 0.97 g / cm ³ (b) Melt flow rate (MFR) 0.01 to 50 g / 10 min (c) Molecular weight distribution (Mw / Mn) 1.5 to 4.5 (d) Composition distribution parameter (Cb) 2.00 or less (C) A polypropylene resin sheet comprising a resin composition containing 0 to 45% by weight of an ethylene polymer. In the ethylene (co) polymer (B), the amount X (Wt%) of orthodichlorobenzene (ODCB) -soluble component at 25 ° C. (e) and the density d and MFR preferably satisfy the following relationships: ) The value of the density d and MFR is d−0.008 × log
When MFR ≧ 0.93 X <2.0 2) The value of the density d and MFR is d−0.008 × log
In case of MFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008
XlogMFR) ² +2.0 More preferably, (f) continuous temperature rising elution fractionation method (TRE).
It is desirable that the elution temperature-elution amount curve according to F) has a plurality of peaks.

The second aspect of the present invention is that (A) the propylene-based polymer (95 to 50% by weight), (B) the ethylene (co) polymer (5 to 50% by weight), and (C) another ethylene-based polymer (0).
A polypropylene resin sheet comprising a resin composition in which 0.01 to 2 parts by weight of the (D) nucleating agent is mixed with 100 parts by weight of the resin component of 45% by weight (however, A + B + C is 100% by weight). is there.

The present invention will be described in more detail below. The (A) propylene-based polymer forming the composition of the present invention is
Propylene homopolymer, propylene and α-olefin block copolymer, propylene and α-olefin random copolymer and the like. The copolymer is propylene and has 2 carbon atoms.
To 8 (excluding 3 carbon atoms) α-olefin copolymer with one or more kinds, particularly preferably propylene / ethylene random copolymer, propylene / ethylene / butene-1 random copolymer They are a combination, a propylene / butene-1 random copolymer, and a propylene / ethylene random copolymer. The propylene polymer is polymerized by a known technique using a Ziegler-Natta type catalyst.

The content of ethylene and butene-1 in the above copolymer is preferably 0.3 to 20% by weight, respectively. When the content of α-olefin is less than 0.3% by weight, the impact strength is not sufficient. Also, the content of α-olefin is 20% by weight.
If it exceeds, the rigidity is low and there is a possibility that the sheet 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 minutes,
It is more preferably 0.3 to 20 g / 10 min. If the MFR is less than 0.1 g / 10 minutes, the fluidity is poor and molding becomes difficult. If it exceeds 30 g / 10 minutes, 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 ethylene (co) polymer (B) of the present invention is an ethylene homopolymer or ethylene and α having 3 to 20 carbon atoms.
-It is a copolymer with one or more kinds selected from olefins. The α-olefin having 3 to 20 carbon atoms is preferably 3 to 12 and specifically, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1 -Decene, 1-dodecene and the like. In addition, it is desirable that the total content of these α-olefins is selected in the range of usually 30 mol% or less, preferably 3 to 20 mol%.

The specific (B) ethylene (co) polymer of the present invention has (a) a density of 0.86 to 0.97 g / cm ³ , preferably 0.89 to 0.95 g / cm ³ . is there.
If the density is less than 0.86 g / cm ³ , the rigidity and heat resistance are poor, and if it is 0.97 g / cm ³ or more, the impact resistance is insufficient. The (B) ethylene (co) polymer (b) melt flow rate is 0.01 to 50, preferably 0.03 to
It is in the range of 30 g / 10 minutes. If the MFR is less than 0.01, the moldability will be poor, and if it is 50 g / 10 minutes or more, the strength will be reduced.

(C) M of the ethylene (co) polymer of the present invention
w / Mn is 1.5 to 4.5, preferably 1.8 to
It is desirable to be in the range of 4.0, preferably 2.0 to 3.5. If Mw / Mn is less than 1.5, the moldability is poor, and if it is 4.5 or more, impact resistance may be poor.
Molecular weight distribution (Mw / M of ethylene (co) polymer of the present invention
The calculation method of n) is to obtain the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC), and then obtain the ratio Mw / Mn.

The (d) composition distribution of the ethylene (co) polymer of the present invention is 2.00 or less, and in the case of the copolymer, 1.
It is in the range of 08 to 2.00, preferably 1.10 to 10.
It is desirable to be in the range of 1.80, and more preferably 1.12 to 1.70. When the (d) composition distribution of the copolymer is less than 1.08, the sheet moldability is poor and 2.00
In the above, there is a possibility that no remarkable improvement in mechanical strength can be expected. Therefore, when the composition distribution is 1.30 or less, it is desirable to add the after-mentioned (C) ethylene polymer.

The method for measuring the composition distribution parameter of the ethylene (co) polymer 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 the sample on the Celite surface. Next, while flowing ODCB at a constant flow rate, the column temperature was increased to 5
The temperature is raised step by step to 120 ° C. to elute the sample and separate the sample. After reprecipitating the solution with methanol, filtration,
Dry to obtain a sample at each elution temperature. The weight fraction and the degree of branching (the number of branches per 1000 carbon atoms) of each sample are measured. The degree of branching (measured value) is determined by 13 C-NMR.

For the fraction of 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 large enough. The value obtained from this calibration curve is defined as the degree of branching 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 of each fraction
The _i, the amount of change in the degree of branching _{b i} per the elution temperature 5 ° C. _{(b i}
-Bi _-1 ) to obtain the relative concentration c _i , and plot the relative concentration against the branching degree to obtain a composition distribution curve. This composition distribution curve is divided by a certain width, and the composition distribution parameter Cb is calculated from the following equation.

[0017]

[Equation 1] Here, C _j and b _j are the relative density and the branching degree of the j-th section, respectively. The 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 separated sample obtained by solvent-separating the sample, and the weight average branching degree (CW)
And the ratio of the number average branching degree (Cn). The accuracy of this approximation calculation decreases when the number of branches and the cumulative weight fraction of the sample deviate from the lognormal distribution, and when a commercially available LLDPE is measured, the correlation coefficient R2 is considerably low, 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 ODCB-soluble content (X% by weight) of the ethylene (co) polymer of the present invention at 25 ° C. is measured by the following method. After adding 0.5 g of the sample to 20 ml of ODCB and heating at 135 ° C. for 2 hours to completely dissolve the sample, 2
Cool to 5 ° C. After leaving this solution at 25 ° C. overnight, the filtrate is collected by filtration through a Teflon filter. Wave number of asymmetric stretching vibration of methylene in sample solution 2925 cm ^-1
The area of the absorption peak in the vicinity is obtained, and the sample concentration is calculated from the calibration curve prepared in advance. From this value, the ODCB-soluble matter at 25 ° C. is determined.

The ethylene (co) polymer of the present invention is preferably (e) the amount X (wt%) of orthodichlorobenzene (ODCB) -soluble content at 25 ° C. and the densities d and M.
FR has a density d and MFR of d-0.008 × l
X is less than 2% by weight when ogMFR ≧ 0.93 is satisfied, and X <9.8 × 103 × (0.9300−d +) when d−0.008 × logMFR <0.93.
0.008 × logMFR) ² +2.0, more preferably, if the values of the density d and MFR satisfy d−0.008 × logMFR ≧ 0.93, X is 1% by weight. Is less than and d-0.008 × log
When MFR <0.93, X <7.4 × 103 ×
(0.9300-d + 0.008 × logMFR) ² +
1.0, more preferably density d and MFR
When the value of d satisfies the condition of d-0.008 × logMFR ≧ 0.93, X is less than 0.5% by weight, and d-0.00.
If 8 × log MFR <0.93, X <5.6 × 1
03 x (0.9300-d + 0.008 x logMF
It is desirable that the relationship R) ² +0.5 is satisfied.

The ortho-dichloroben-soluble component at 25 ° C. is a highly branched component and a low molecular weight component contained in the polymer, which causes a decrease in heat resistance and stickiness on the surface of the molded article, so that its content is small. Is desirable. ODC
The amount of B-soluble component is influenced by the content and molecular weight of comonomer. Therefore, these indicators of density and MFR
The fact that the amounts of ODCB and ODCB-soluble matter satisfy the above relationship indicates that the proportion of the comonomer copolymerized in the highly branched component of the polymer is small.

When the component (B) of the present invention is an ethylene copolymer, it is preferable that there are a plurality of peaks in the elution temperature-elution amount curve obtained by (f) continuous temperature rising elution fractionation method (TREF). , The elution temperature of these is 85 ℃ to 1
It is particularly preferred that there is a peak between 00 ° C. The presence of this peak improves the heat resistance and rigidity of the molded body. Further, FIG. 1 shows an elution temperature-elution amount curve of the copolymer of the present invention, and FIG. 2 shows an elution temperature-elution amount curve of a copolymer with a typical metallocene catalyst. As is clear from this figure, the ethylene copolymer as the component (B) of the present invention is clearly distinguished from the metallocene-catalyzed ethylene-α-olefin copolymer.

Continuous temperature rising elution fractionation method (T
The measurement method of REF) 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 0.05% by weight. 5 ml of the sample solution is injected into a column filled with glass beads and cooled to 25 ° C. at a cooling rate of 0.1 ° C./min to deposit the sample on the surface of the glass beads. Next, the column temperature is raised at a constant rate of 50 ° C./hr while flowing ODCB at a constant flow rate through this column, and the sample is sequentially eluted. At this time, for the sample eluted in the solvent, the wavenumber 292 of the asymmetric stretching vibration of methylene was measured.
Absorption at 5 cm ⁻¹ is detected by an infrared detector and quantitatively distributed. From this value, the weight concentration of PE in the solution is quantitatively analyzed to determine the relationship between the elution temperature and the elution rate. Since the TREF analysis can analyze the change of the elution rate with respect to the temperature change continuously with a very small amount of sample, it is possible to detect relatively fine peaks that cannot be detected by the fractionation method.

The specific ethylene (co) polymers of the present invention are
It has the properties (i) to (d) above, and preferably (e)
Although it is only necessary to further satisfy the property (f), it is preferable to polymerize with the catalyst consisting of the following E1 to E5.

That is, E1: general formula Me ¹ R ¹ _p (O
R < ² _> ) _qX < ¹ _{> 4-pq The} compound (in formula, Me)
¹ represents Zr, Ti, and Hf, R ¹ and R ² each represent a hydrocarbon group having 1 to 24 carbon atoms, X 1 represents a halogen atom, and p, q, and r each represent 0 ≦ p <4, 0 < p + q. ≦ 4
Is an integer) which satisfies a range of, E2: general formula _{^{Me 2 R 3 m (OR 4}} ) n X 2 z-m-n
A compound represented by the formula (wherein Me ² is I to III in the periodic table).
Group ³ elements, R ³ and R ⁴ are each a hydrocarbon group having 1 to 24 carbon atoms, X ² is a halogen atom or a hydrogen atom (provided that X is
² represents a hydrogen atom, Me ² represents a group III element of the periodic table), z represents the valence of Me ² , and m and n each represent 0 ≦ m ≦ z and 0 < n ≦. z is an integer satisfying the range of z, and 0 ≦ m + n ≦ z), E3: an organic cyclic compound having a conjugated double bond, and E4: an Al—O— obtained by a reaction of an organoaluminum compound and water. Modified organoaluminum compound containing Al bond, E5: A catalyst obtained by bringing an inorganic carrier and / or a particulate polymer carrier into contact with each other.

The above catalyst component (E1) has the general formula Me ¹ R ¹
Me < ¹ > shows Zr, Ti, and Hf in the formula of the compound represented by _p (OR < ² >) _qX < ¹ _{> 4-} pq. The type of these transition metals is not limited, and a plurality thereof can be used, but it is particularly preferable that Zr, which has excellent weather resistance of the copolymer, is contained. R ¹ and R ² each have 1 to 24 carbon atoms
A hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group; a vinyl group or an allyl group. Alkenyl groups such as groups; aryl groups such as phenyl, tolyl, xylyl, mesityl, indenyl, naphthyl; benzyl, trityl, phenethyl, styryl, benzhydryl, phenylbutyl, neofil, etc. And the aralkyl group of. These may have branches. X
¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p and q are 0 ≦ p <4 and 0 < q <, respectively.
4, satisfying a range of 0 ≦ p + q ≦ 4, preferably 0 ≦ p
The range is + q ≦ 4.

Examples of the compound represented by the above general formula of the catalyst component (El) include tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, dipropoxydichlorozirconium,
Examples thereof include tetrabutoxyzirconium, tributoxymonochlorozirconium, dibutoxydichlorozirconium, tetrabutoxytitanium, and tetrabutoxyhafnium. These may be used as a mixture of two or more.

The above catalyst component (E2) has the general formula Me ² R ³
_m ^(OR ₄₎ wherein Me ² in n ^X compounds represented by _{2 z-m-n} represents the periodic table I~III group element, lithium, sodium, potassium, magnesium, calcium, zinc, boron, Such as aluminum. R ³ and R ⁴ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, Alkyl groups such as butyl group; alkenyl groups such as vinyl group, allyl group; aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, naphthyl group; benzyl group, trityl group, phenethyl group, styryl group And aralkyl groups such as benzhydryl group, phenylbutyl group, and neophyll group. These may have branches. X ² represents a halogen atom such as fluorine, iodine, chlorine and bromine, or a hydrogen atom. However, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table exemplified by boron, aluminum and the like. Further, z represents the valence of Me ² , m and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 < n ≦ z, and 0 ≦ m + n ≦ z.

Examples of the compound represented by the general formula of the catalyst component (E2) include organolithium compounds such as methyllithium and ethyllithium; dimethylmagnesium, diethylmagnesium, methylmagnesium chloride,
Organomagnesium compounds such as ethylmagnesium chloride; Organozinc compounds such as dimethylzinc and diethylzinc; Organoboron compounds such as trimethylboron and triethylboron; Trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethyl Examples thereof include derivatives of organic aluminum compounds such as aluminum chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum ethoxide and diethyl aluminum hydride.

The organic cyclic compound having a conjugated double bond of the catalyst component (E3) is a cyclic ring having two or more conjugated double bonds, preferably 2 to 4 and more preferably 2 to 3. It has 1 or 2 or more, and the total carbon number is 4 to 2.
4, preferably 4 to 12 cyclic hydrocarbon compounds; wherein the cyclic hydrocarbon compounds are partially 1 to 6 hydrocarbon residues (typically, alkyl groups or aralkyl groups having 1 to 12 carbon atoms) A cyclic hydrocarbon compound substituted by; a compound having 2 or more, preferably 2 to 4, more preferably 2 to 3 rings having a conjugated double bond and having a total carbon number of 4 to 24 An organosilicon compound having a cyclic hydrocarbon group which is preferably 4 to 12; said cyclic hydrocarbon group being partly substituted with 1 to 6 hydrocarbon residues or an alkali metal salt (sodium or lithium salt) Includes organosilicon compounds. Particularly preferably, those having a cyclopentadiene structure in any of the molecules are desirable.

Examples of the preferred compounds include cyclopentadiene, indene, azulene and their alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives. Moreover, the compound which these compounds couple | bonded (bridge | crosslink) through the alkylene group (The carbon number is 2-8 normally, Preferably 2-3) is also used suitably.

The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula.

[0033]

[Equation 2] Here, A represents the cyclohydrogen group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R represents a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. An alkyl group such as a group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; an aryl group such as a phenyl group; an aryloxy group such as a phenoxy group; an aralkyl group such as a benzyl group having 1 carbon atom ~ 24, preferably 1-12 hydrocarbon residues or hydrogen, L is 1
≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

Specific examples of the organic cyclic hydrocarbon compound of the above component (E3) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, 4, 7-Dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene-containing cyclopolyene or substituted cyclopolyene, monocyclopentadienylsilane, biscyclo Examples thereof include pentadienylsilane, triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane, and trisindenylsilane.

The modified organoaluminum compound containing the Al--O--Al bond obtained by the reaction of the catalyst component (E4) organoaluminum compound with water is usually an aluminoxane by reacting an alkylaluminum compound with water. A so-called modified organoaluminum is obtained, and usually 1 to 100, preferably 1 to 50 Al in the molecule.
It contains a —O—Al bond. The modified organoaluminum compound may be linear or cyclic.

The reaction between the organoaluminum and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon,
Aliphatic, alicyclic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene are preferred. The reaction ratio between water and the organoaluminum compound (water / Al molar ratio) is usually 0.25 / 1 to 1.2.
/ 1, preferably 0.5 / 1 to 1/1.

The catalyst component (E5) inorganic carrier and / or particulate polymer carrier means a carbonaceous material, a metal, a metal oxide, a metal chloride, a metal carbonate or a mixture thereof, or a thermoplastic resin, a thermosetting resin or the like. Is mentioned. Suitable metals that can be used for the inorganic carrier include:
Examples include iron, aluminum, and nickel. Specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO
_{2, B 2 O 3, CaO} , ZnO, BaO, ThO 2 and the like or mixtures _thereof, SiO 2 -Al
₂ O ₃ , SiO ₂ —V ₂ O ₅ , SiO ₂ —TiO ₂ , S
_{iO 2 -V 2 O 5, SiO} 2 -MgO, SiO 2 -Cr
₂ O _{3 and the} like. Among these, those containing, as a main component, at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ . Further, as the organic compound, any of a thermoplastic resin and a thermosetting resin can be used. Specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, polymethyl (meth) acrylate, polystyrene, poly Examples include norbornene, various natural polymers, and mixtures thereof.

The above-mentioned inorganic carrier and / or particulate polymer carrier can be used as they are, but preferably, as a pretreatment, the carrier is an organoaluminum compound or a modified organoaluminum compound containing an Al--O--Al bond. It can also be used as the component (E5) after being contact-treated with.

The method for producing the ethylene / α-olefin copolymer (B) of the present invention is a gas phase method, a slurry method, a solution method or the like, and is not particularly limited such as a one-step polymerization method and a multi-step polymerization method. However, the gas phase method is particularly preferable.

The other ethylene-based polymer (C) components used in the present invention are roughly classified into two types, and the first component (C1) is a Ziegler-based catalyst or Cr-based catalyst by a conventional ionic polymerization method. An ethylene polymer or an ethylene / α-olefin copolymer having a density of 0.86 to 0.97 g / cm ³ obtained by (hereinafter collectively referred to as Ziegler type catalyst), and specifically, high density polyethylene (HDP
E), 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) produced by 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 minutes, preferably 0.1 to
10 g / 10 minutes, more preferably 0.3 to 10 g / 1
It is selected in the range of 0 minutes. 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 1.
It is generally 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 minutes,
It is preferably selected in the range of 0.1 to 10 g / 10 minutes. The ultra-low density polyethylene (VLDPE) is a polyethylene having an intermediate property between linear low-density polyethylene (LLDPE) and ethylene / α-olefin copolymer rubber (EPR, EPDM), and is a differential scanning calorimeter. (DSC) maximum peak temperature (Tm) 60 ° C or higher,
And a specific ethylene / α-olefin copolymer having a boiling n-hexane insoluble content of 10% by weight or more, and a catalyst comprising a solid catalyst component containing at least titanium and / or vanadium and an organoaluminum compound. It is a resin that is polymerized by using a combination of the high crystalline part of linear low-density polyethylene and the amorphous part of ethylene / α-olefin copolymer rubber, and has the characteristics of the former such as mechanical strength and heat resistance. Properties, the latter characteristics such as rubber elasticity and low temperature impact resistance coexist in a well-balanced manner.

Ethylene / α-by the above Ziegler type catalyst
The α-olefin of the olefin copolymer has 3 to 12 carbon atoms, preferably 3 to 10 carbon atoms,
Specific examples thereof include propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1. 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) is 0.05 to 20 g / 10
Min, preferably 0.1 to 10 g / 10 min, 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 to 0.94 g / cm
³ , preferably 0.912 to 0.935 g / cm ³ , and more preferably 0.912 to 0.930 g / cm ³ . Further, Mw / Mn is 3.0 to 12, preferably 4.
It is 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 trifluone acetate. Among these, vinyl acetate can be mentioned as a particularly preferable one. That is, a copolymer comprising 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. In particular, 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 minutes, preferably 0.3.
It is about 10 g / min.

Representative copolymers of the ethylene / α, β-unsaturated carboxylic acid or its derivative of the present invention 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, n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate,
Glycidyl acrylate, glycidyl methacrylate and the like can be mentioned. Among these, alkyl esters of (meth) acrylic acid such as methyl and ethyl are particularly preferable. In particular, the content of the (meth) acrylate 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 / min.

(A), (B), (C) of the composition of the present invention
The mixing ratio of each resin component is as follows. (A) Propylene polymer: 95-50% by weight, preferably 93-60% by weight, more preferably 87-65% by weight (B) Ethylene (co) polymer: 5-50% by weight, preferably 7- 40% by weight, more preferably 13 to 35% by weight (C) Other ethylene polymer: up to 45% by weight, preferably up to 35% by weight, more preferably up to 30% by weight. When the content of (B) is 5% by weight or less, the effect of modifying the propylene-based polymer is not recognized, and mechanical properties such as impact strength and optical properties such as haze cannot be expected to increase. Further, when the content of (B) is 50% by weight or more, the characteristics of the propylene-based polymer are deteriorated and the rigidity and the like are deteriorated,
It is unsuitable for seat applications. 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.

The nucleating agent (D) used in the present invention means transparency,
It is used for improving rigidity and the like, and examples thereof include a sorbitol compound, a metal salt of a carboxylic acid, an aromatic phosphate ester compound, an inorganic compound of silica and talc.

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.

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-
Mention may be made of t-butyl aluminum benzoate and the like.

The aromatic phosphoric acid ester compound specifically has a structure represented by the following general formulas (1) to (7).

[0053]

Embedded image (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.)

[0054]

Embedded image (In the formula, R ₃ and R ₄ represent a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, and R ₅ represents a hydrogen atom or 1 to 4 carbon atoms.
Is an alkyl group. Further, M ₂ represents a metal atom of Group I, Group II, or Group III of the periodic table, and a represents a valence of M ₂ .

[0055]

Embedded image (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, an aryl group or an aralkyl group. Indicates.

[0056]

Embedded image

[0057]

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

[0058]

[Chemical 6] (In the formula, each R ₁₄ is a hydrogen atom or 1 to
4 represents an alkyl group, 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, and Y represents M ₃ Is an —OH group when Group III is a periodic table, and M ₃ is an —OH group or a — (OH) ₂ group when Group ₃ is a group IV of the periodic table. )

[0059]

[Chemical 7] (In the formula, each R ₁₇ is a hydrogen atom or a carbon number 1
4 is an alkyl group, and R ₁₈ and R ₁₉ are each a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group,
An aryl group, an aralkyl group, Z is -OH group or ^-O - shows the _NH ^{4 +} group. )

Typical examples of commercially available aromatic phosphoric acid ester compounds represented by the above formulas 1 to 7 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 carboxylic acid, aromatic phosphoric acid ester compound and inorganic compound are used. Among them, the aromatic phosphoric acid ester compound is most preferably used because it has little odor.

The amount of these nucleating agents added is 100
0.01 to 2 parts by weight, preferably 0.0
3 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, containers such as blister packs, or 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 for construction, civil engineering and industrial materials. The thickness is 05 to 5 mm, preferably 0.1 to 3 mm, and more preferably 0.2 to 2 mm.

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

[0065]

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. The following were used as the components (A), (B), (C) and (D).

Component (A): <Propylene polymer> Al: Propylene-ethylene random copolymer with Ziegler catalyst (MFR = 1.5 g / 10 minutes, trade name: Nisseki Polypro E420G, Nippon Petrochemical Co., Ltd.) A2: Propylene homopolymer with Ziegler catalyst (M
FR = 1.8 g / 10 minutes, product name: Nisseki Polypro E12
0G, manufactured by Nippon Petrochemical Co., Ltd.) A3: propylene-ethylene block copolymer with a Ziegler catalyst (MFR = 0.5 g / 10 minutes, trade name: Nisseki Polypro E610G, manufactured by Nippon Petrochemical Co., Ltd.)

Component (B): <Ethylene (co) polymer> used in Examples and Comparative Examples was polymerized by the following method. (Preparation of Solid Catalyst) Purified toluene was added to the catalyst preparation device 1 with an electromagnetic induction stirrer under nitrogen, 28 g of dipropoxydicrocozirconium (Zr (OPr) ₂ Cl ₂ ) and 48 g of methylcyclopentadiene were added, and the mixture was added at 0 ° C. While maintaining the system, 45 g of tridecylaluminum was added dropwise, and after completion of the addition, the reaction system was maintained at 50 ° C. and stirred for 16 hours. This solution is designated as solution A. Next, under nitrogen, purified toluene was added to another catalyst preparation device 2 with a stirrer, and the solution A was added, and then a toluene solution of 6.4 mol of methylaluminoxane was added and reacted. This is designated as solution B. Next, purified toluene was added to the preparer 1 with a stirrer under nitrogen, and then the silica was preliminarily calcined at 400 ° C. for a predetermined time (Fuji Devison Co., grade # 952, surface area 300).
m ² / g) 1400 g was added, and then the whole amount of the solution B was added and stirred at room temperature. Then, the solution was removed by nitrogen blowing to obtain a solid catalyst powder having good fluidity. This is designated as a catalyst Cat.

(Polymerization of Sample B1) Using a continuous fluidized bed gas phase polymerization apparatus, the polymerization temperature was 70 ° C. and the total pressure was 20 kgf / c.
Copolymerization of ethylene and 1-butene was carried out with m ² G. The gas composition in the system is 1-butene / ethylene molar ratio 0.12,
The ethylene concentration was 60 mol%. The catalyst Cat was continuously supplied to carry out polymerization, and each gas was continuously supplied to keep the gas composition in the system constant. The physical properties of the produced copolymer are shown in Table 1.

(Polymerization of Samples B2 and B4) Polymerization was carried out in the same manner as in (B1) except that the molar ratio of 1-butene / ethylene was changed. The physical properties of the copolymer are shown in Table 1 together with the experimental results.

(Polymerization of Sample B3) (B3) was polymerized in the same manner as in (B1) except that 1-hexene was used as the comonomer. The physical properties of the copolymer are shown in Table 1 together with the experimental results.
It was shown to.

Samples (B5) and (B6) used other than the above
Is LLDPE obtained by copolymerizing ethylene and 1-butene or 1-hexene by a gas phase method or a slurry method using titanium tetrachloride and triethylaluminum catalyst. Further, (B7) is a commercially available Ultzex 3010F (manufactured by Mitsui Petrochemical Co., Ltd.). Its physical properties are shown in Table 1 together with the experimental results.
~ Shown in Table 3.

Component (C): <Ethylene Polymer> C1-1: Ziegler-catalyzed linear low-density polyethylene (density = 0.928 g / cm ³ , MFR = 0.9 g /
10 minutes, comonomer: 1-butene Nippon Petrochemical Co., Ltd.
C1-2: Ultra low density polyethylene by Ziegler catalyst (density = 0.900 g / cm ³ , MFR = 0.5 g / 1
0 minutes, comonomer: 1-butene 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 phosphate 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. Al-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: According to JIS K 6760 MFR: Polypropylene polymer JIS K 675
8: Ethylene polymer conforms to JIS K6760 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. DuPont impact tester Izod impact: conforming to JIS K6758 Haze: direct reading haze meter according to JIS K7105 (suga test) Machine HGH-2DP type)

[Examples 1 to 14, Comparative Examples 1 to 5] The components (A), (B), (C) and (D) described above are shown in Tables 1 to 1.
Each composition was prepared by mixing with the general-purpose stirrer in the blending amount shown in Table 2. 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 (for measuring all haze) 1.0 mm (for measuring DuPont impact and bending stiffness) In Comparative Example 3, since the sheet molding was defective,
The molding resin temperature was 240 ° C. <Heat Press Sheet Molding> 230 ° C. Thickness 6.0 mm (for Izod Impact Measurement) The performance of each sheet was measured by the evaluation method described above. Table 1 shows the results.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

The polypropylene-based resin sheet obtained by the composition of the present invention has the following features. Mechanical strength such as impact strength is remarkably higher than conventional polypropylene resin sheets, and sheets made of polypropylene homopolymer or propylene / ethylene random copolymer composition have excellent optical properties and excellent transparency. is there.

[Brief description of drawings]

FIG. 1 shows an elution temperature-elution amount curve of the copolymer of the present invention.

FIG. 2 shows an elution temperature-elution amount curve of a copolymer with a metallocene catalyst.

Claims (9)

[Claims] 1. An (A) propylene-based polymer of 95 to 50% by weight, (B) an ethylene (co) polymer of 5 to 50% by weight which satisfies the following (A) to (D) (B) density of 0.86 ~ 0.97 g / cm ³ (b) Melt flow rate (MFR) 0.01 to 50 g / 10 min (c) Molecular weight distribution (Mw / Mn) 1.5 to 4.5 (d) Composition distribution parameter (Cb) A polypropylene resin sheet made of a resin composition containing 2.00 or less. 2. The (B) ethylene (co) polymer,
(E) Ortho-dichlorobenzene (ODC at 25 ° C)
B) The polypropylene resin sheet according to claim 1, wherein the amount X (Wt%) of the soluble component and the densities d and MFR satisfy the following relationships. 1) Density d and MFR values are d-0.008 × log
When MFR ≧ 0.93 X <2.0 2) The value of the density d and MFR is d−0.008 × log
In case of MFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008
× logMFR) ² +2.0 3. The ethylene (co) polymer (B) is
(F) The polypropylene-based resin sheet according to claim 1 or 2, wherein the elution temperature-elution amount curve has a plurality of peaks by a continuous temperature rising elution fractionation method (TREF). 4. The (A) propylene polymer 95 to 5
0% by weight and (B) ethylene (co) polymer 5 to 50% by weight
And (C) the other ethylene-based polymer up to 45% by weight (provided that the total of A + B + C is 100% by weight), the polypropylene-based resin according to any one of claims 1 to 3. Sheet. 5. The polypropylene resin according to claim 1, wherein 0.01 to 2 parts by weight of the nucleating agent (D) is mixed with 100 parts by weight of the resin component. Sheet. 6. The propylene polymer (A) is a propylene homopolymer, a propylene-ethylene random copolymer, or a mixture thereof, according to any one of claims 1 to 5. The polypropylene-based resin sheet described. 7. The polypropylene-based resin sheet according to claim 1, wherein the propylene-based polymer (A) is a propylene-ethylene block copolymer. 8. The (C) other ethylene-based polymer is at least one kind selected from the following ethylene-based polymers. Polypropylene resin sheet. (C-1) Density by Ziegler type catalyst 0.86-0.
97 g / cm ³ ethylene homopolymer or ethylene
α-olefin copolymer (C-2) low-density polyethylene by high-pressure radical polymerization, ethylene / vinyl ester copolymer, ethylene /
Copolymer with α, β-unsaturated carboxylic acid or its derivative 9. The (D) nucleating agent is at least one selected from talc, an organic carboxylic acid or a metal salt thereof, a metal salt of an organic phosphate, and a sorbitol-based compound. Item 10. The polypropylene-based resin sheet according to any one of Items 1 to 8.