CN108219295A - Polypropene composition, polypropylene film-making material and its manufacturing method and secondary forming body - Google Patents

Abstract

The present invention provides the excellent impact resistance under a kind of transparency, rigidity, heat resistance, uniform extensibility and low temperature, and the biaxial stretched polypropylene film-making material with easy hot-forming property and its manufacturing method and uses secondary forming body (container etc.) and the polypropene composition suitable for manufacturing the sheet material obtained by sheet material progress hot forming.The polypropene composition of the present invention is characterized in that：Include acrylic polymer and crystallization nucleating agent containing ethylene, the ethylene contents for containing the acrylic polymer of ethylene are less than dimethylbenzene insoluble component amount when 1 mass %, molecular weight distribution (Mw/Mn) be 6~20,25 DEG C more than 96.5 mass % and below 99.5 mass % and the stereoregularity of dimethylbenzene insoluble component (mmmm) is 97.5%~99.5%, for the crystallization nucleating agent relative to above-mentioned 100 mass parts of acrylic polymer containing ethylene and less than 0.18 mass parts, melt flow rate (MFR) is 1g/10 minutes~15g/10 minutes.

Description

Polypropene composition, polypropylene film-making material and its manufacturing method and secondary forming body

Technical field

Polypropylene film-making material, the polypropylene film-making the present invention relates to polypropene composition, comprising the polypropene composition The secondary forming body of the manufacturing method of material and the polypropylene film-making material.

Background technology

Polypropylene is cheap, and rigid, moisture-proof and excellent heat resistance, is suitable as food packaging or fiber package The material of sheet material used in dress etc..For example, existing use the container for applying polypropylene as the food containers with heat resistance, But there are problems in terms of intensity, in order to make up the problem, and container are made to have thickness or adds in a large amount of flank to cope with, But cost increase can be led to the problem of or content does not see Chu.In addition, in order to confirm the content in food containers, and want The transparency is sought, but polypropylene is crystalline resin, is originally used for translucent sheet material, therefore be used as its improvement alternative, it is known that Add crystallization nucleating agent.But nonetheless, it is also difficult to obtain enough transparencys.In addition, in recent years in order to cope with freezing shape Circulation under state, and require that also there is impact resistance even in a low temperature of -30 DEG C.

It proposes addition in order to improve in the transparency of the formed products of polypropene composition, such as patent document 1 and crystallizes into The method of core agent.In addition, as the method for improving polyacrylic rigidity or the transparency, there is known the method (patents extended Document 2).Moreover, in order to improve the balance of rigidity and the transparency, and the method for utilizing the combination of polypropene composition is also known (patent document 3).But the formed body for the polypropene composition being achieved in that is at low temperature in use, there are impact resistance drops The problem of low.In order to improve the above problem, such as propose and vinyl copolymer (patent document 4) is added in polypropylene.

Existing technical literature

Patent document

Patent document 1：International Publication No. 2013/125504

Patent document 2：Japanese patent application public affairs table 2004-517199 bulletins

Patent document 3：Japanese patent application discloses 2009-242672 bulletins

Patent document 4：Japanese patent application public affairs table 2011-513528 bulletins.

Invention content

The subject that the invention solves

However according to the discovery of the inventors of the present invention, in the method for patent document 1, it is difficult to while realize high transparency, height High-impact under rigidity and low temperature, and be also difficult to assign uniform extensibility and easy hot-forming property simultaneously.

In addition, usually known extended polypropylene sheet material has biaxial stretched polypropylene sheet material, but usually with vertical × horizontal stroke=5 × 10 times or so of high magnification is extended.However according to the discovery of the inventors of the present invention, if to be fitted with this high magnification In hot formed sheet thickness (0.1mm~0.5mm), then a sheet thickness before extension must be set as 5mm~25mm, and The making of sheet material is extremely difficult.Even if it assuming that realizes the making of a sheet material of above-mentioned thickness and is manufactured and extended with high magnification Sheet material, also due to the sheet material increase of stress or morphotropism in elongation reduce and wire drawing formability (hot-forming property) reduction, because This is configured to can be extremely difficult as the shape of mold.On the other hand, it is manufactured to make a thickness thinning with low range When extending sheet material, it can generate and extend uneven (became uneven) caused by constriction (necking), cause because being heated during forming Product stability caused by unevenness reduces, and product can not be configured to by leading to the problem of.As described in Patent Document 2, also have to double Axis extends formability and balances the case improved, but can be insufficient using this prior art formability with rigid, can not The good sheet material of thickness precision is obtained, rigidity is also not as good as the present invention.It in addition, can not be to being drawn using the sheet material that this method makes Silk forming (hot forming).

In addition, in the method for patent document 3, although utilizing the polypropylene group being such as suitble to the sheet forming technique of the prior art The specific combination of object is closed, the rigid sheet material with the balancing good of the transparency can be made, but not only not as good as the rigidity of the present invention and thoroughly The balance of bright property, and can not assign the high-impact under low temperature using this method.

In addition, as the method for patent document 4, impact resistance under low temperature can be assigned by adding vinyl copolymer Property, but the transparency reduce, therefore using this method obtain polypropylene-based sheet material, without it is satisfactory the transparency with it is cold-resistant The balance of impact.

The present invention is to solve the inventions of the subject of the prior art as described above, provide a kind of transparent, rigid, heat-resisting Property, the excellent impact resistance under uniform extensibility and low temperature, and the biaxial stretched polypropylene film-making material with easy hot-forming property, The secondary forming body (container etc.) of the hot formed no problem on using is carried out using the sheet material and suitable for manufacturing the sheet material Polypropene composition.

The means to solve the problem

The inventors of the present invention make great efforts to study in order to solve the above problems and with keen determination, as a result, it has been found that, using with particular range Molecular weight distribution, crystallinity, stereoregularity, melt flow rate (MFR), ethylene contents are less than specific quantity, and crystallization nucleating agent contains Amount extends manufacture sheet material, thus to obtain rigidity, the uniformly transparency, extension less than the polypropene composition of specific quantity by twin shaft Property, cold temperature impact, easy hot-forming property the extremely excellent sheet material of balance, in addition, by by the sheet material of the present invention carry out heat into Shape, and the secondary forming body of the physical property for maintaining sheet material and excellent heat resistance is obtained, so as to complete the present invention.

The present invention has implementation below.

[1] a kind of polypropene composition, it is characterised in that：Include acrylic polymer and crystallization nucleation containing ethylene Agent, the ethylene contents for being somebody's turn to do the acrylic polymer containing ethylene are less than 1 mass %, molecular weight distribution (Mw/Mn) is 6~20,25 Dimethylbenzene insoluble component amount at DEG C is more than 96.5 mass % and below 99.5 mass % and the vertical structure of dimethylbenzene insoluble component is advised Whole property (mmmm) is 97.5%~99.5%, and the crystallization nucleating agent is relative to above-mentioned 100 matter of acrylic polymer containing ethylene Part is measured less than 0.18 mass parts, melt flow rate (MFR) is 1g/10 minutes~15g/10 minutes.

[2] polypropene composition according to [1], wherein, following crystallization rate parameter (t_1/2) more than 1 second；Crystallization speed Spend parameter (t_1/2)：The 1/2 required time of Mixed Growth is reached when crystallizing for 120 DEG C.

[3] polypropene composition according to [1] or [2], wherein, the catalyst comprising following component is used, is made Propylene and vinyl polymerization and obtain：(A) make containing the electron donor compound selected from magnesium, titanium, halogen and succinate based compound Solid catalyst for essential component；(B) organo-aluminum compound；And (C) external electron-donor compound.

[4] a kind of polypropylene film-making material, it is characterised in that：It is as the polypropylene group described in any one of above-mentioned [1] to [3] The sheet material that object is formed is closed, wherein thickness is 100 μm~500 μm, is stretched in tension test when thickness precision is less than 12 μm, 160 DEG C Long strain more than 200% and during elongation 200% stress be less than 10MPa, tensile modulus of elasticity at 23 DEG C more than 1800MPa ,- Face impact strength at 30 DEG C is more than 2J, and mist degree is less than 2.5%, is more than 60% using the image definition that through transmission technique obtains.

[5] a kind of manufacturing method of polypropylene film-making material, it is characterised in that：It is poly- according to above-mentioned [4] for manufacturing Propylene film-making material, including that will not extend the step of sheet material carries out twin shaft extension, this does not extend sheet material by above-mentioned polypropylene group Object is closed to form.

[6] according to the manufacturing method of the polypropylene film-making material described in [5], wherein, forming temperature when above-mentioned twin shaft extends It it is 140 DEG C~170 DEG C, forming speed is 20%/second~400%/second, and the extension ratio in MD directions and TD directions is respectively 3 times ~6 times.

[7] a kind of secondary forming body, it is characterised in that：Will according to the polypropylene film-making material described in above-mentioned [4] carry out heat into Shape forms.

The effect of invention

According to the present invention, the excellent impact resistance under the transparency, rigidity, heat resistance, uniform extensibility and low temperature can be obtained, And the biaxial stretched polypropylene film-making material with easy hot-forming property.

The polypropene composition of the present invention is suitable for manufacturing the biaxial stretched polypropylene film-making material.

The excellent heat resistance of the secondary forming body of the present invention.

Specific embodiment

＜ measuring methods ＞

Each physics value in the present invention is as described below.

[thickness of sheet material and thickness precision]

The thickness of polypropylene film-making material and thickness precision are using the continuous thickness gauge (TOF- that mountain message gas company manufactures 4R05), the average value when the width direction of sheet material is using more than 100 points of 1mm interval measurements is thickness, standard deviation (μm) Value for thickness precision.

Thickness accuracy value is smaller, then it represents that uneven thickness is smaller, during for extension sheet material, then it represents that uniform extensibility is more excellent It is different.

[tensile modulus of elasticity]

The tensile modulus of elasticity of polypropylene film-making material is according to JIS K7161-1, with drawing in the environment for being 23 DEG C in room temperature Speed is stretched for the 1mm/ minutes values being measured.Tensile modulus of elasticity value is bigger, then rigidity is more excellent.

[face impact strength]

The face impact strength of polypropylene film-making material is according to JIS K7211-2, and (the straight of facet is beaten with the striker of cylindrical shape Diameter is 12.7mm), test speed carved to carry out within 1m/ second beating at -30 DEG C, calculate puncture energy (unit：J (joule)) obtained by Value.Puncture energy value is bigger, then face impact strength is more excellent.

[mist degree]

The mist degree of polypropylene film-making material is the value according to obtained by ISO 14782 measures mist degree.Haze value is smaller, then transparent It is more excellent.

[image definition (transparency) obtained using through transmission technique]

The image definition (hereinafter also referred to as transparency) obtained using through transmission technique of polypropylene film-making material, be utilize according to The value being measured according to the method for ASTM D 1746.Transparence value is bigger, then obscures and feel fewer, the transparency is more excellent.

[stress when extension strain and elongation]

Stress during extension strain and elongation about polypropylene film-making material, sheet material cuts out 2 type of JIS K7127 types after extension Short strip shape test film (width 10mm × length 150mm), between collet distance as 100mm, tensile speed be 500mm/ minutes into Row tension test.It measures temperature and is set as 160 DEG C, the relationship of stress and strain is obtained.

If extension strain value at 160 DEG C is big and the value of stress during elongation 200% at 160 DEG C is small, easily heat into Shape (secondary forming property) is excellent.

[load deformation temperature]

Using forming temperature as 160 DEG C by polypropylene film-making material hot forming, make width 120mm × length 170mm × depth The container of 27mm.This container is being stood 1 hour in advance as defined in being set as in the thermostat of environment temperature, after 1 hour, By top surface entire to container apply it is loaded in a manner of, mounting 400g counterweights confirm top surface whether there is deformation.With the side of 5 DEG C of grades Formula improves environment temperature, using temperature when deforming as load deformation temperature.Load deformation temperature is higher, then heat resistance (heat-resisting rigidity) is more excellent.

[molecular weight distribution (Mw/Mn)]

The molecular weight distribution of polymer or copolymer (Mw/Mn) is to measure matter average molecular weight using gel permeation chromatography (Mw) and number-average molecular weight (Mn) value obtained by, calculating Mw/Mn.

The PL GPC220 that device is manufactured using Polymer Laboratory company, by 1 comprising antioxidant, 2,4- trichloro-benzenes As mobile phase, tubing string uses the UT-G (1) for manufacturing Showa electrician company, UT-807 (1), UT-806M (2) tandem The tubing string of connection, detector use differential refraction rate meter.In addition, the solvent of the sample solution of polypropene composition is used and is flowed Mutually identical solvent under the sample concentration of 1mg/mL, at a temperature of 150 DEG C, dissolves the survey of 2 hour adjustments while vibrating Measure sample.Thus obtained 500 μ L of sample solution are injected into tubing string, by 1.0mL/ of flow velocity minute, temperature be 145 DEG C, Data are divided into 1 second between obtaining and measure.The correction of tubing string uses the polystyrene standard sample that molecular weight is 5,800,000~7,450,000 Product (Shodex STANDARD, Showa Denko K. K's manufacture), are carried out with cubic expression tertiary approximation.About polystyrene standard sample Product, the coefficient of Mark-Houkins use K=1.21 × 10^-4, α=0.707, about the acrylic polymer containing ethylene, The coefficient of Mark-Houkins uses K=1.37 × 10^-4, α=0.75.

[amount of dimethylbenzene insoluble component]

Stirring 2.5g polymer on one side, makes it be dissolved in 250ml dimethylbenzene at 135 DEG C on one side.It stirs on one side after twenty minutes Solution is mixed, is cooled to 25 DEG C on one side, then static 30 minutes.Sediment is filtered with filter paper, solution is made to be evaporated in nitrogen stream, It is dried at 80 DEG C under vacuum until residue reaches constant weight.Dimethylbenzene is dissolved in when calculating 25 DEG C in this way Soluble polymer quality %.The amount of dimethylbenzene insoluble component is (insoluble in the insoluble polymer of dimethylbenzene at 25 DEG C Quality %), it is obtained by (the quality % of 100- soluble polymers), it is considered that be the amount of the isotaxy ingredient of polymer.

About dimethylbenzene insoluble component, will be remained in after the dimethylbenzene on sediment fully rinses with methanol, under vacuum It is dried and acquires at 80 DEG C.

[steric regularity (tacticity) mmmm of dimethylbenzene insoluble component]

About the mmmm of dimethylbenzene insoluble component obtained in aforementioned manners, to being dissolved in 1,2,4- trichloro-benzenes/deuterate benzene In the mixed solvent sample, according to use Japan Electronics Corporation manufacture JNM LA-400 (¹³C resonant frequencies are 100MHz), It utilizes¹³The spectrum that C-NMR methods measure, according to A.Zambelli, Macromolecules, 6, the method described in 925 (1973), The ratio of the peak strength of five unit groups for being equivalent to 4 meso (m) key sequences and continuously forming of propylene monomer is obtained.

[melt flow rate (MFR) (MFR)]

The melt flow rate (MFR) of polypropene composition be according to JIS K7210, temperature be 230 DEG C, load 21.18N Under conditions of the value that measures.

[crystallization rate parameter (t_1/2) measuring method]

Crystallization rate parameter (the t of polypropene composition_1/2) it is to use thermal compensation type Differential Scanning Calorimetry measuring device (example Such as, Perkinelmer Inc. manufacture diamond DSC) measure, 120 DEG C crystallize when reach Mixed Growth 1/2 needed for The time wanted.t_1/2Value it is bigger, then it represents that carrying out for crystallization is slower.Specifically, sample will be measured temporarily to melt at 280 DEG C It solves and keeps after five minutes, kept for 15 minutes until 80 DEG C/min are cooled to 120 DEG C and with isothermal.By relatively therebetween etc. The time that temperature crystallizes caused whole calorific values (being equivalent to Mixed Growth) and reaches 1/2 calorific value is set as t_1/2。

＜ polypropylene film-making materials ＞

The polypropylene film-making material (hereinafter also referred to as " this sheet material ") of the present invention includes the polypropene composition of the present invention.It closes In the polypropene composition of the present invention, described below.This sheet material can be individual layer or multilayer laminated object.

The thickness of this sheet material is 100 μm~500 μm, preferably 100 μm~300 μm.If thickness is 100 μm or more, Formability when this sheet material figuration being made secondary forming product is good.If thickness be 500 μm hereinafter, if can easily carry out It is secondary forming.When thickness to be obtained is more than 500 μm of sheet material, the collet that sheet material is clamped when twin shaft extends and is kept comes off, And it can not easily carry out twin shaft extension.

The thickness precision of this sheet material is less than 12 μm, preferably smaller than 8 μm.If thickness precision is above range, to this film Formability when material figuration is made secondary forming product is good.It can be by reducing thickness accuracy value, to improve this sheet material or its is secondary The appearance and impact resistance of formed products.The lower limit of the thickness precision is simultaneously not limited.It is alternatively 0.It is 2 μm or more Zuo You in reality.

In tension test of this sheet material preferably at 160 DEG C, extension strain is more than 200%, and stress is small during elongation 200% In 10MPa.If stress is in above range, when secondary forming product are made to this sheet material figuration when the extension strain and elongation Formability it is good.

Tensile modulus of elasticity of this sheet material at 23 DEG C is more than 1800MPa, preferably greater than 2500MPa.If the stretching bullet Property modulus be above range, then sheet material excellent rigidity.It is in addition, in the wrong by being difficult to generate in the secondary forming product of this sheet material figuration It is bent.The upper limit of the tensile modulus of elasticity is simultaneously not limited.It is below 3100MPa left and right in reality.

Face impact strength of this sheet material at -30 DEG C is more than 2J.If the face impact strength is above range, this sheet material Or its excellent strength of secondary formed products at low temperature, it is difficult to crack.The upper limit of the face impact strength is simultaneously not limited.Reality In for below 30J left and right.

The mist degree of this sheet material is less than 2.5%, preferably smaller than 2%.If mist degree is above range, this sheet material or its is secondary The transparency of formed products is excellent.The lower limit of mist degree is simultaneously not limited.It is more than 0.5% Zuo You in reality.

The transparency of this sheet material is more than 60%, preferably more than 70%.If transparency is above range, this sheet material Or the transparency of its secondary formed products is excellent.The upper limit of transparency is simultaneously not limited.It is less than 99% Zuo You in reality.

Secondary forming product obtained by this sheet material is carried out hot forming, the load deformation temperature preferably as Heat-tolerant index are 110 DEG C or more, more preferably 120 DEG C or more.If the load deformation temperature is above range, the heat resistance of secondary forming product It is excellent.The upper limit of the load deformation temperature is simultaneously not limited.It is less than 150 DEG C Zuo You in reality.

＜ polypropene compositions ＞

This sheet material is that the polypropene composition of the present invention is configured to sheet and is obtained.

The polypropene composition of the present invention (in this specification, referred to as " contains second comprising the acrylic polymer containing ethylene The acrylic polymer of alkene ").

The Mw/Mn of acrylic polymer containing ethylene is 6~20, has relatively broad molecular weight distribution.If The Mw/Mn is more than the lower limiting value of above range, then is easy to get excellent thickness precision, if the Mw/Mn is more than upper limit value, It is then difficult to manufacture the acrylic polymer containing ethylene.

The amount of the dimethylbenzene insoluble component of acrylic polymer containing ethylene, more than 96.5 mass % and 99.5 mass % Below.The polyacrylic ingredient insoluble in dimethylbenzene is equivalent to crystalline isotaxy ingredient.In contrast, polypropylene In the ingredient for dissolving in dimethylbenzene that includes on a small quantity, be equivalent to without crystalline atactic ingredient, and insoluble in diformazan The ingredient of benzene is compared, and molecular weight is also low.Therefore, the physical property of the melting characteristic of polypropylene-based resin material or formed products mainly by Ingredient insoluble in dimethylbenzene restricts.The amount of the dimethylbenzene insoluble component of polypropylene-based resin material be more than 96.5 mass % and 99.5 mass % hereinafter, be represent polypropylene-based resin material crystallinity ingredient be more than 96.5 mass % and 99.5 mass % with Under.

When the crystallinity ingredient of the acrylic polymer containing ethylene is below 96.5 mass %, will particularly include poly- The rigidity of (secondary) formed products and heat resistance obtained by the sheet material of propylene compositions carries out hot forming, particularly rigidity reduce.Contain The amount for having the dimethylbenzene insoluble component of the acrylic polymer of ethylene is preferably greater than 97.0 mass % and below 99.5 mass %.

The stereoregularity (mmmm) of the crystallinity ingredient of acrylic polymer containing ethylene is 97.5%~99.5%. When mmmm is less than 97.5%, (secondary) formed products obtained by the sheet material comprising polypropene composition particularly is carried out hot forming Rigidity and heat resistance, particularly heat resistance reduce.

Ethylene contents in acrylic polymer containing ethylene are less than 1 mass %, preferably smaller than 0.6 mass %.Ethylene Content more preferably less than 0.3 mass %.Acrylic polymer containing ethylene be make ethylene and propylene carry out random copolymerization and The polymer obtained.By the way that ethylene and propylene is made to carry out random copolymerization, the transparency improves.If the propylene polymerization containing ethylene Ethylene contents in object are less than 1 mass %, then are easy to get excellent rigidity.The lower limit of the ethylene contents is not particularly limited, For more than 0 mass %.In terms of the improvement effect for easily fully obtaining the transparency, preferably more than 0.1 mass %.

The MFR of the polypropene composition of the present invention is 1g/10 minutes~15g/10 minutes, preferably 2g/10 minutes~6g/ 10 minutes.If the MFR is in above range, having excellent formability when polypropene composition is configured to sheet.

The polypropene composition of the present invention preferably comprises crystallization nucleating agent.The addition of crystallization nucleating agent helps to improve transparent Property.The concrete example of crystallization nucleating agent is described below.

Relative to 100 mass parts of acrylic polymer containing ethylene in polypropene composition, crystallization nucleating agent contains Amount is less than 0.18 mass parts, and preferably 0.15 is below mass part.If the content of the crystallization nucleating agent is less than above-mentioned upper limit value, It is easy to get excellent thickness precision.The lower limit of the crystallization nucleation agent content is not particularly limited, for more than 0 mass %.From saturating From the point of view of in terms of bright property improvement effect, which is preferably more than 0.01 mass parts.

The preferred crystallization rate parameter (t of polypropene composition of the present invention_1/2) more than 1 second, more preferably 2 seconds or more.When subtracting During the additive amount of few crystallization nucleating agent, there are crystallization rate reduction, (t_1/2) increased tendency.

It if should (t_1/2) more than above-mentioned lower limiting value, then it is easy to get excellent thickness precision.It should (t_1/2) the upper limit have no It is particularly limited to, is less than 5 seconds Zuo You in reality.

[crystallization nucleating agent]

Crystallization nucleating agent is preferably selected from：Nonoses alcohol (nonitol) is nucleating agent, D-sorbite system nucleating agent, phosphate system Nucleating agent, triaminobenzene derivatives nucleating agent, carboxylic metallic salt nucleating agent and xylitol system nucleating agent.Particularly for raising The purpose of the transparency more preferably uses nonoses alcohol system's nucleating agent or D-sorbite system nucleating agent.

Crystallization nucleating agent with nonoses alcohol architecture can for example be enumerated：Tri- deoxidations -4,6 of 1,2,3-:5,7- is bis--[(4- third Base phenyl) methylene]-nonoses alcohol；Crystallization nucleating agent with xylitol architecture can for example be enumerated：Double -1,3:2,4-(5', 6', 7', 8'- tetrahydrochysene -2- naphthaldehydes benzal) -1- allyls xylitol, double -1,3:2,4- (3', 4'- dimethyl benzylidene)- 1- propyl xylitols；Crystallization nucleating agent with D-sorbite architecture can for example be enumerated：Double -1,3:2,4- (4'- ethylbenzylidenes Base) -1- pi-allyls D-sorbite, double -1,3:2,4- (the fluoro- benzals of 3'- methyl -4'-) -1- propyl D-sorbite, double -1,3: 2,4- (3', 4'- dimethyl benzylidene) -1'- methyl -2'- acrylic D-sorbite, double -1,3,2,4- dibenzylidenes -2', 3'- Dibromopropyl D-sorbite, the bromo- 3'- hydroxypropyls D-sorbites of double -1,3,2,4- dibenzylidenes -2'-, double -1,3:2,4- (the bromo- 4'- ethylbenzylidenes of 3'-) -1- pi-allyls D-sorbite, list 2,4- (the bromo- 4'- ethylbenzylidenes of 3'-) -1- pi-allyls mountain Pears sugar alcohol, double -1,3:2,4- (4'- ethylbenzylidenes) -1- pi-allyls D-sorbite, double -1,3:(3', 4'- dimethyl are sub- by 2,4- Benzyl) -1- methyl D-sorbite, bis- (to methylbenzilidene) D-sorbites, 1,3:2,4- is bis--neighbour (4- methylbenzilidenes)-D- D-sorbite etc..

The commercially available crystallization nucleating agent of nonoses alcohol system used in the composition of the present invention can for example be enumerated：Millad NX8000 (Japanese Milliken)；The commercially available crystallization nucleating agent of D-sorbite system can be enumerated：RiKAFAST R-1 (new Japan Chemical), Millad 3988 (Japanese Millikens), GEL ALL E-200 (new Japan Chemical), GEL ALL MD (new Japan Chemical) etc..

Phosphate system crystallization nucleating agent can be enumerated：Bis- (tetra--tertiary butyl of 4,4', 6,6'- -2,2'- methylenediphenyls-phosphorus Acid)-aluminium hydroxide etc..Commercially available phosphate system crystallization nucleating agent used in the composition of the present invention can for example be enumerated：ADK STAB (ア ス カ ス タ Block) NA-21 (ADEKA), ADK STAB NA-71 (ADEKA) etc..Triaminobenzene derivatives crystallization nucleating agent example It can such as enumerate：1,3,5- tri- (2,2- dimethylpropionamides) benzene etc..Commercially available triaminobenzene used in the composition of the present invention derives Object crystallization nucleating agent can for example be enumerated：IRGACLEAR XT386 (Japanese BASF) etc..Carboxylic metallic salt nucleating agent can be enumerated： 1,2- cyclohexane cyclohexanedimethanodibasic calcium salts etc..Commercially available carboxylic metallic salt nucleating agent used in the composition of the present invention can for example be enumerated： Hyperform HPN-20E (Japanese Milliken) etc..

Especially for the transparency after maintenance secondary operation (heating), it is preferable to use nonoses alcohol system's nucleating agent or sorbose Alcohol system nucleating agent.

These crystallization nucleating agents may be used alone or in combination two or more uses.

[other additives]

The present invention polypropene composition in, within the scope of the effect of the invention, can contain crystallization nucleating agent with Other outer additives.

The example of other additives can be enumerated：Antioxidant, neutralizer, chlorine absorbent, heat-resisting stabilizing agent, light stabilizer, Ultra-violet absorber, internal lubricant, exterior lubricant, antitack agent, antistatic agent, antifoggant, fire retardant, dispersant, copper are blunt Agent, plasticiser, crosslinking agent, peroxide, oil-filled (oil-extended) agent and other organic and inorganic pigments etc. are usually used In the typical additives of polyolefin.The additive amount of each additive can be set as well known amount.

[manufacturing method of polypropene composition]

The polypropene composition of the present invention is to manufacture the acrylic polymer containing ethylene, mixed crystallization nucleation as needed Agent and other additives and obtain.

The manufacturing method of acrylic polymer containing ethylene is not particularly limited, the method for preferably including following steps： Using comprising following (A) ingredients, (B) ingredient, (C) ingredient catalyst component, propylene and ethylene is made to carry out combined polymerization.

(A) ingredient：Contain the electricity selected from magnesium, titanium, halogen and succinate based compound as electron donor compound Solid catalyst of the sub- compound donator as essential component.

(B) ingredient：Organo-aluminum compound.

(C) ingredient：External electron-donor compound selected from silicon compound.

1) solid catalyst (ingredient A)

Ingredient (A) can be by well known method, such as makes magnesium compound, titanium compound and electron donor compound mutual It contacts and prepares.

What the titanium compound used in the preparation of ingredient (A) was suitble to has general formula：Ti(OR)_gX_4-g4 shown valency titanium compounds. In formula, R is alkyl, X is halogen, 0≤g≤4.Titanium compound can more specifically be enumerated：TiCl₄、TiBr₄、TiI₄Wait titanium tetrahalides； Ti(OCH₃)Cl₃、Ti(OC₂H₅)Cl₃、Ti(O_n-C₄H₉)Cl₃、Ti(OC₂H₅)Br₃、Ti(OisoC₄H₉)Br₃Deng three halogenated alkoxies Titanium；Ti(OCH₃)₂Cl₂、Ti(OC₂H₅)₂Cl₂、Ti(O_n-C₄H₉)₂Cl₂、Ti(OC₂H₅)₂Br₂Wait dihalogenated alkoxytitaniums；Ti (OCH₃)₃Cl、Ti(OC₂H₅)₃Cl、Ti(O_n-C₄H₉)₃Cl、Ti(OC₂H₅)₃The one halogenation tri-alkoxy titanium such as Br；Ti(OCH₃)₄、Ti (OC₂H₅)₄、Ti(O_n-C₄H₉)₄Etc. tetraalkoxy titaniums etc..It is preferably the titanium compound containing halogen, particularly four halogenations in these Titanium, more preferably titanium tetrachloride.

Magnesium compound used in the preparation of ingredient (A) can be enumerated：Magnesium compound with magnesium-carbon key or magnesium-hydrogen bond, such as Dimethyl magnesium, magnesium ethide, dipropyl magnesium, dibutylmagnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethylmagnesium chloride, third Base magnesium chloride, butylmagnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl magnesium ethylate, ethyl-butyl magnesium, butyl magnesium hydride Deng.These magnesium compounds use in the form of complex that also can be by with organo-aluminium, in addition, these magnesium compounds can be Liquid or solid-state.The magnesium compound being more suitable for can be enumerated：The halogen as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride Change magnesium；As methoxy magnesium chloride, ethyoxyl magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octyloxy magnesium chloride Alkoxymagnesium halides；The aryloxymagnesium halides magnesium as phenoxy group magnesium chloride, methylphenoxy magnesium chloride；As magnesium ethylate, Alkoxyl magnesium as isopropoxy magnesium, butoxy magnesium, n-octyloxy magnesium, 2- ethyl hexyl oxy magnesium；Such as phenoxy group magnesium, dimethyl Aryloxy group magnesium as phenoxy group magnesium；Carboxylate of magnesium etc. as Magnesium dilaurate, magnesium stearate.

Electron donor compound used in the preparation of ingredient (A) is commonly known as " Internal electron donors ".In the present invention, It is preferable to use the Internal electron donors for providing broad molecular weight distribution.Use the composition that the catalyst is polymerize and such as the following group Conjunction object, which is compared, shows different characteristics：To use that the polymer that other catalyst polymerize carries out particle or powder mixes and Composition obtain, that there is identical molecular weight distribution；Or it utilizes multistep polymerization method or utilizes and use with monomer concentration or gather The method of the polymerizer of the gradient of conjunction condition, the composition with identical molecular weight distribution being polymerize.Its reason is generally recognized For in the composition manufactured using the catalyst, high molecular weight components and low molecular weight compositions are in the shape closer to molecular level It is integrally formed under state, but the resin combination of the latter not mixes in the state of the molecular level for being close to that degree, only Identical molecular weight distribution is but shown on apparent.But it is not existing to show such case with word in the claims Real.Hereinafter, preferred Internal electron donors are illustrated.

Preferred Internal electron donors are succinate based compound in the present invention.So-called succinate system in the present invention Object is closed, refer to the diester of succinic acid or replaces the diester of succinic acid.Hereinafter, succinate based compound is described in detail. In the present invention it is preferable to use succinate based compound by following formula (I) expression.

In formula, group R₁And R₂It is mutually identical or different, according to circumstances to include heteroatomic C₁~C₂₀Threadiness or branch Alkyl, alkenyl, cycloalkyl, aryl, aryl alkyl or alkylaryl；Group R₃~R₆It is mutually identical or different, it is hydrogen or root According to situation to include heteroatomic C₁~C₂₀Threadiness or branch alkyl, alkenyl, cycloalkyl, aryl, aryl alkyl or alkyl Aryl, the group R being bonded on same carbon atom or different carbon atoms₃~R₆Ring can be bonded together to form together.

R₁And R₂Preferably C₁~C₈Alkyl, cycloalkyl, aryl, aryl alkyl and alkylaryl.Particularly preferred R₁And R₂ Compound selected from primary alkyl, particularly branch's primary alkyl.Suitable R₁And R₂The example of group is C₁~C₈Alkyl, such as For methyl, ethyl, n-propyl, normal-butyl, isobutyl group, neopentyl, 2- ethylhexyls.Particularly preferred ethyl, isobutyl group and new penta Base.

It is by one of preferred group of formula (I) compound represented：R₃~R₅For hydrogen, R₆To have the branch of 3~10 carbon atoms Alkyl, cycloalkyl, aryl, aryl alkyl and alkylaryl compound.The preferred tool of this monosubstituted succinate compound Body example is：Sec-butyl diethyl succinate, hexyl diethyl succinate, cyclopropyl diethyl succinate, norborny succinic acid Diethylester, perhydro diethyl succinate, trimethylsilyl diethyl succinate, methoxyl group diethyl succinate, to methoxyl group Phenylsuccinic acid diethylester, rubigan diethyl succinate, phenylsuccinic acid diethylester, cyclohexyl diethyl succinate, benzyl Base diethyl succinate, cyclohexyl methyl diethyl succinate, tertiary butyl diethyl succinate, isobutyl group diethyl succinate, Isopropyl diethyl succinate, neopentyl diethyl succinate, isopentyl diethyl succinate, (1- trifluoromethyls ethyl) amber Diethyl phthalate, fluorenyl diethyl succinate, phenylsuccinic acid 1- ethyoxyl carbon diisobutyl ester, sec-butyl di-iso-octyl succinate, Hexyl di-iso-octyl succinate, cyclopropyl di-iso-octyl succinate, norborny di-iso-octyl succinate, perhydro succinic acid two are different Butyl ester, trimethylsilyl di-iso-octyl succinate, methoxyl group di-iso-octyl succinate, two isobutyl of p-methoxyphenyl succinic acid Ester, rubigan di-iso-octyl succinate, cyclohexyl di-iso-octyl succinate, benzyl di-iso-octyl succinate, cyclohexyl methyl Di-iso-octyl succinate, tertiary butyl di-iso-octyl succinate, isobutyl group di-iso-octyl succinate, two isobutyl of isopropyl succinic acid Ester, neopentyl di-iso-octyl succinate, isopentyl di-iso-octyl succinate, (1- trifluoromethyls ethyl) di-iso-octyl succinate, Fluorenyl di-iso-octyl succinate, two peopentyl ester of sec-butyl succinic acid, two peopentyl ester of hexyl succinic acid, cyclopropyl succinic acid two new penta Ester, two peopentyl ester of norborny succinic acid, two peopentyl ester of perhydro succinic acid, two peopentyl ester of trimethylsilyl succinic acid, methoxy Two peopentyl ester of base succinic acid, two peopentyl ester of p-methoxyphenyl succinic acid, two peopentyl ester of rubigan succinic acid, phenylsuccinic acid Two peopentyl esters, two peopentyl ester of cyclohexyl succinic acid, two peopentyl ester of benzyl succinic acid, two peopentyl ester of cyclohexyl methyl succinic acid, uncle Two peopentyl ester of butyl succinic acid, two peopentyl ester of isobutyl group succinic acid, two peopentyl ester of isopropyl succinic acid, neopentyl succinic acid two are new Pentyl ester, two peopentyl ester of isopentyl succinic acid, two peopentyl ester of (1- trifluoromethyls ethyl) succinic acid, two peopentyl ester of fluorenyl succinic acid.

Other preferred groups of compound in the range of formula (I) are：From R₃~R₆At least two group and hydrogen it is different, root According to situation include it is heteroatomic, selected from C₁~C₂₀Threadiness or the alkyl of branch, alkenyl, cycloalkyl, aryl, aryl alkyl or The compound of alkylaryl.Compound of 2 particularly preferably different with the hydrogen group bondings on same carbon atom.Specifically： R₃And R₄For the group different with hydrogen, R₅And R₆Compound for hydrogen atom.This two substitutions preferred concrete example of succinate It is：2,2- dimethylsuccinics diethyl phthalate, 2- Ethyl-2-Methyls diethyl succinate, 2- benzyl -2- isopropyl succinic acid diethyls Ester, 2- cyclohexyl methyl -2- isobutyl groups diethyl succinate, 2- cyclopenta -2- normal-butyls diethyl succinate, bis- isobutyls of 2,2- Base diethyl succinate, 2- cyclohexyl -2- ethylsuccinic acids diethylester, 2- isopropyl -2- methyl succinics diethyl phthalate, 2- 14 Alkyl -2- ethylsuccinic acids diethylester, 2- isobutyl group -2- ethylsuccinic acids diethylester, 2- (1- trifluoromethyls ethyl) -2- methyl Diethyl succinate, 2- isopentyl -2- isobutyl groups diethyl succinate, 2- phenyl -2- normal-butyls diethyl succinate, 2,2- bis- Methylsuccinic acid diisobutyl ester, 2- Ethyl-2-Methyls di-iso-octyl succinate, 2- benzyl -2- isopropyls di-iso-octyl succinate, 2- cyclohexyl methyl -2- isobutyl groups di-iso-octyl succinate, 2- cyclopenta -2- normal-butyls di-iso-octyl succinate, 2,2- bis- are different Butyl di-iso-octyl succinate, 2- cyclohexyl -2- ethylsuccinic acids diisobutyl ester, two isobutyl of 2- isopropyl -2- methylsuccinic acids Ester, 2- myristyl -2- ethylsuccinic acids diisobutyl ester, 2- isobutyl group -2- ethylsuccinic acids diisobutyl ester, 2- (1- fluoroforms Base ethyl) -2- methylsuccinic acids diisobutyl ester, 2- isopentyl -2- isobutyl groups di-iso-octyl succinate, 2- phenyl -2- normal-butyls Di-iso-octyl succinate, two peopentyl ester of 2,2- dimethyl succinates, two peopentyl ester of 2- Ethyl-2-Methyls succinic acid, 2- benzyls -2- Two peopentyl ester of isopropyl succinic acid, two peopentyl ester of 2- cyclohexyl methyl -2- isobutyl groups succinic acid, 2- cyclopenta -2- normal-butyl ambers Two peopentyl esters of amber acid, two peopentyl ester of 2,2- diisobutyls succinic acid, two peopentyl ester of 2- cyclohexyl -2- ethylsuccinic acids, 2- isopropyls Two peopentyl ester of base -2- methylsuccinic acids, two peopentyl ester of 2- myristyl -2- ethylsuccinic acids, 2- isobutyl group -2- ethylsuccinic acids Two peopentyl esters, two peopentyl ester of 2- (1- trifluoromethyls ethyl) -2- methylsuccinic acids, 2- isopentyl -2- isobutyl groups succinic acid two are new Pentyl ester, two peopentyl ester of 2- phenyl -2- normal-butyls succinic acid.

Moreover, the also particularly preferred compound of at least two group bonding different with hydrogen on different carbon atoms.Specifically It is：R₃And R₅Compound for the group different with hydrogen.At this point, R₄And R₆Can be hydrogen atom or the base different with hydrogen Group, but preferably any one is hydrogen atom (three substitution succinates).This preferred concrete example of compound is：2,3- bis- (three Methyl-monosilane base) diethyl succinate, 2,2- sec-butyl -3- methyl succinics diethyl phthalate, 2- (3,3,3- trifluoro propyls) -3- first Bis- (2- ethyl-butyls) diethyl succinates of base diethyl succinate, 2,3-, 2,3- diethyl -2- isopropyl succinic acid diethyls Ester, 2,3- diisopropyl -2- methyl succinics diethyl phthalate, 2,3- dicyclohexyl -2- methyl succinics diethyl phthalate, 2,3- dibenzyl Bis- (cyclohexyl methyl) diethyl succinates of diethyl succinate, 2,3- diisopropyls diethyl succinate, 2,3-, bis- uncles of 2,3- Butyl diethyl succinate, 2,3- diisobutyls diethyl succinate, 2,3- di neo-pentyls diethyl succinate, 2,3- diisoamyls Base diethyl succinate, 2,3- (1- trifluoromethyls ethyl) diethyl succinate, 2,3- myristyls diethyl succinate, 2,3- Fluorenyl diethyl succinate, 2- isopropyl -3- isobutyl groups diethyl succinate, 2- tertiary butyl -3- isopropyls diethyl succinate, 2- isopropyl -3- cyclohexyl diethyl succinate, 2- isopentyl -3- cyclohexyl diethyl succinate, 2- myristyl -3- hexamethylenes Ylmethyl diethyl succinate, 2- cyclohexyl -3- cyclopenta diethyl succinate, 2,3- diethyl -2- isopropyls succinic acid two Isobutyl ester, 2,3- diisopropyl -2- methylsuccinic acids diisobutyl ester, 2,3- dicyclohexyl -2- methylsuccinic acids diisobutyl ester, 2, Bis- (cyclohexyl methyl) succinic acids two of 3- dibenzyl di-iso-octyl succinate, 2,3- diisopropyls di-iso-octyl succinate, 2,3- Isobutyl ester, 2,3- di-t-butyls di-iso-octyl succinate, 2,3- diisobutyls di-iso-octyl succinate, 2,3- di neo-pentyl ambers Sour diisobutyl ester, 2,3- diisoamyl di-iso-octyl succinate, 2,3- (1- trifluoromethyls ethyl) di-iso-octyl succinate, 2,3- Myristyl di-iso-octyl succinate, 2,3- fluorenyls di-iso-octyl succinate, two isobutyl of 2- isopropyl -3- isobutyl groups succinic acid Ester, 2- tertiary butyl -3- isopropyls di-iso-octyl succinate, 2- isopropyl -3- cyclohexyl di-iso-octyl succinate, 2- isopentyl - 3- cyclohexyl di-iso-octyl succinate, 2- myristyl -3- cyclohexyl methyls di-iso-octyl succinate, 2- cyclohexyl -3- rings penta Bis- two peopentyl esters of (trimethylsilyl) succinic acid of base di-iso-octyl succinate, 2,3-, 2,2- sec-butyl -3- methylsuccinic acids two Peopentyl ester, two peopentyl ester of 2- (3,3,3- trifluoro propyls) -3- methylsuccinic acids, bis- (2- ethyl-butyls) succinic acids two new penta of 2,3- Ester, two peopentyl ester of 2,3- diethyl -2- isopropyls succinic acid, two peopentyl ester of 2,3- diisopropyl -2- methylsuccinic acids, 2,3- bis- Two peopentyl ester of cyclohexyl -2- methylsuccinic acids, two peopentyl ester of 2,3- dibenzyl succinic acid, 2,3- diisopropyls succinic acid two new penta Bis- two peopentyl esters of (cyclohexyl methyl) succinic acid of ester, 2,3-, two peopentyl ester of 2,3- di-t-butyls succinic acid, 2,3- diisobutyl ambers Two peopentyl esters of amber acid, two peopentyl ester of 2,3- di neo-pentyls succinic acid, two peopentyl ester of 2,3- diisoamyl succinic acid, 2,3- (1- tri- Methyl fluoride ethyl) two peopentyl ester of succinic acid, two peopentyl ester of 2,3- myristyls succinic acid, two peopentyl ester of 2,3- fluorenyls succinic acid, Two peopentyl ester of 2- isopropyl -3- isobutyl groups succinic acid, two peopentyl ester of 2- tertiary butyl -3- isopropyls succinic acid, 2- isopropyl -3- rings Two peopentyl ester of hexyl succinic acid, two peopentyl ester of 2- isopentyl -3- cyclohexyl succinic acid, 2- myristyl -3- cyclohexyl methyl ambers Two peopentyl esters of amber acid, two peopentyl ester of 2- cyclohexyl -3- cyclopenta succinic acid.

In the compound of formula (I), it also may be preferable for use group R₃~R₆In several compounds for bonding together to form ring together. This compound can be enumerated：In the compound cited by Japanese patent application public affairs table 2002-542347, such as 1- (ethyoxyls Carbonyl) -1- (Ethoxyacetyl base) -2,6- dimethyl cyclohexanes, 1- (ethoxy carbonyl) -1- (Ethoxyacetyl base) -2,5- Dimethylcyclopentane, 1- (ethoxy carbonyl) -1- (Ethoxyacetylmethyl) -2- hexahydrotoluenes, 1- (ethoxy carbonyl) - 1- (ethyoxyl (cyclohexyl) acetyl group) hexamethylene.In addition, it for example can also be suitble to use：Such as International Publication No. 2009/069483 The ring-type amber such as disclosed 3,6- dimethyl cyclohexanes -1,2- dioctyl phthalate diisobutyl ester, hexamethylene -1,2- dioctyl phthalate diisobutyl esters Ester compound.The examples of other cyclic annular succinate compounds it is also preferred that：Chemical combination disclosed in International Publication 2009/057747 Object.

In the compound of formula (I), in group R₃~R₆During comprising hetero atom, hetero atom preferably comprises nitrogen-atoms and phosphorus is former 15th race's atom of son or the 16th race's atom including oxygen atom and sulphur atom.Group R₃~R₆Include the chemical combination of the 15th race's atom Object can be enumerated：Japanese patent application discloses compound disclosed in No. 2005-306910.On the other hand, group R₃~R₆Include The compound of 16 race's atoms can be enumerated：Japanese patent application discloses compound disclosed in No. 2004-131537.

In addition, it is possible to use the Internal electron donors with the distribution of succinate based compound equivalent molecule amount are provided.It is this Internal electron donors can for example be enumerated：Japanese patent application discloses the diphenyldicarboxylic acid of 2013-28704 bulletins record Ester, Japanese patent application disclose the cyclohexene dicarboxylic acid ester of 2014-201602 bulletins record, Japanese patent application discloses the The bicyclic alkyl dicarboxylic ester of 2013-28705 bulletins record, the dibenzoic acid glycol of No. 4959920 records of Japanese Patent No. The dibenzoic acid 1,2- benzene diester that ester, International Publication No. 2010/078494 are recorded.

2) organo-aluminum compound (ingredient B)

The organo-aluminum compound of ingredient (B) can enumerate following compound.

The trialkylaluminiums such as triethyl aluminum, tri-butyl aluminum；

The trialkenyl aluminium as three isopentene group aluminium：

The dialkyl group aluminum alkoxides such as diethylaluminum ethoxide, dibutyl butoxy aluminium；

The alkyl sesquialter aluminum alkoxides such as ethyl sesquialter aluminum ethoxide, butyl sesquialter butoxy aluminium；

The parts halogen such as alkyl dihalides aluminium as ethylaluminum dichloride, propyl al dichloride, butyl aluminum dibromide etc. The alkyl aluminum of change；

The dialkyl group aluminum hydride such as diethylaluminum hydride, dibutyl aluminum hydride；

The partially hydrogenated alkyl aluminums such as the alkyl aluminum dihydrides such as ethyl dihydroaluminium, propyl aluminum dihydride；

Parts alkoxylate and the halogen such as ethyl ethyoxyl aluminium chloride, butyl butoxy aluminium chloride, ethyl ethyoxyl aluminium bromide The alkyl aluminum of change.

3) electron donor compound (ingredient C)

The electron donor compound of ingredient (C) is commonly known as " external electron-donor ".This electron donor compound is excellent Select organo-silicon compound.Preferred organo-silicon compound can enumerate following compound.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyl diethoxy silicon Alkane, diisopropyl dimethoxy silane, tertbutyl methyl dimethoxysilane, tertbutyl methyl diethoxy silane, tertiary pentyl Methyldiethoxysilane, dimethoxydiphenylsilane, phenyl methyl dimethoxysilane, diphenyl diethoxy silane, Double o-tolyl dimethoxysilanes, it is double between tolyl dimethoxysilane, double p-methylphenyl dimethoxysilanes, double to toluene Base diethoxy silane, double ethylphenyl dimethoxysilanes, dicyclopentyl dimethoxyl silane, dicyclohexyl dimethoxy silicon Alkane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl methyl diethoxy silane, ethyl trimethoxy silane, three ethoxy of ethyl Base silane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyl triethoxysilane, decyl trimethoxy silicon Alkane, decyl triethoxysilane, phenyltrimethoxysila,e, γ-r-chloropropyl trimethoxyl silane, methyltriethoxysilane, Ethyl triethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, hexyl trimethoxy silane, positive fourth Ethyl triethoxy silicane alkane, isobutyl triethoxy silane, phenyl triethoxysilane, γ aminopropyltriethoxy silane, chlorine Triethoxysilane, three isopropoxy silane of ethyl, vinyltributoxysilane, cyclohexyl trimethoxy silane, cyclohexyl Triethoxysilane, 2- norbornanes trimethoxy silane, 2- norbornanes triethoxysilane, 2- norbornane methyl dimethoxies Oxysilane, silester, butyl silicate, trimethyl phenoxysilane, methyl triolefin the npropoxysilane, (β-first of vinyl three Oxygroup Ethoxysilane), vinyltriacetoxy silane, dimethyl tetraethoxy disiloxane.

Wherein preferably：Ethyl triethoxysilane, n-propyl triethoxysilane, n-propyl trimethoxy silane, tertiary fourth Ethyl triethoxy silicane alkane, tertbutyl methyl dimethoxysilane, tertbutyl methyl diethoxy silane, t-butylethyl dimethoxy Base silane, tertiary butyl propyldimethoxy-silane, tertiary butyl tert-butoxy dimethoxysilane, tert-butyl trimethoxy silane, Trimethoxysilane, isobutyl methyl dimethoxysilane, butyl sec-butyl dimethoxysilane, (perhydro is different for ethyl Quinoline -2- bases) dimethoxysilane, bis- (Decahydroisoquinolinpreparation -2- bases) dimethoxysilanes, three (isopropyl alkenyloxy group) phenyl silicon Alkane, hexyl trimethoxy silane, vinyltriethoxysilane, phenyl triethoxysilane, phenyltrimethoxysila,e, ethylene Three butoxy silane of base, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Isobutyl group isopropyl dimethoxysilane, cyclopenta tert-butoxy dimethoxysilane, dicyclopentyl dimethoxyl silane, hexamethylene Ylmethyl dimethoxysilane, cyclohexyl isobutyl group dimethoxysilane, cyclopenta isobutyl group dimethoxysilane, cyclopenta are different Propyldimethoxy-silane, di-sec-butyl dimethoxysilane, diethylamino triethoxysilane, tetraethoxysilane, four It is methoxy silane, isobutyl triethoxy silane, phenyl methyl dimethoxysilane, phenyl triethoxysilane, double to toluene Base dimethoxysilane, p-methylphenyl methyl dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-ethyl dimethoxy Base silane, 2- norbornanes triethoxysilane, 2- norbornanes methyl dimethoxysilane, diphenyl diethoxy silane, Methyl (3,3,3- trifluoro propyls) dimethoxysilane, silester etc..

The catalyst contact for making starting monomer and preparing in the manner as described above is polymerize.At this point, first it is preferable to use Above-mentioned catalyst carries out prepolymerization.So-called prepolymerization is to make polymer chain as the springboard that starting monomer formally polymerize thereafter The step being formed on solid catalyst component.Prepolymerization can be carried out using well known method.Prepolymerization usually below 40 DEG C, Preferably less than 30 DEG C, more preferably less than 20 DEG C progress.

Then, it will be imported into polymerization reaction system through pre-polymerized catalyst, and carry out the formal polymerization of starting monomer.

Method well known to slurry technique (polymerization in liquid monomer) or gas-phase polymerization etc. can be used in polymerization.In addition, Successive polymerization method can also be used in polymerization：Each follow-up polymerization is the polymeric agents formed in its previous polymerisation In the presence of carry out, and have at least two successive polymerization stage.

Chain-transferring agent (such as hydrogen or ZnEt can be used₂) etc. molecular weight regulator well known in the art.

Acrylic polymer containing ethylene is to supply propylene monomer, vinyl monomer, catalyst, basis in the reaction system The molecular weight regulator supplied is needed, propylene monomer and vinyl monomer is made to carry out combined polymerization and obtain.

Polymerization temperature is preferably 40 DEG C~100 DEG C, more preferably 50 DEG C~90 DEG C, especially preferably 60 DEG C~90 DEG C.

About polymerization pressure, when carrying out in the liquid phase, the range of preferably 33bar~45bar (3.3MPa~4.5MPa), It is the range of 5bar~30bar (0.5MPa~3.0MPa) when carrying out in the gas phase.

In addition, the polymerizer of the gradient with monomer concentration or polymerizing condition can be used.In this polymerizer, such as can The polymerizer connected using at least two zone of convergency, by gas-phase polymerization by monomer polymerization.Specifically, exist in catalyst Under, monomer is supplied by the zone of convergency for including tedge and is polymerize, is carried out by the down-comer supply monomer connected with tedge Polymerization, on one side recycles tedge and down-comer, recycles polymer product on one side.This method has comprehensively or partly prevents The admixture of gas being only present in tedge enters the mechanism of down-comer.In addition, will have and be present in tedge The gas and/or liquid mixture of admixture of gas difference composition are imported into down-comer.Above-mentioned polymerization is for example applicable The method that Japanese patent application public affairs table 2002-520426 bulletins are recorded.

When adding crystallization nucleating agent and other additives, machine (Brabender) is reached using Henschel mixer, Bradley sheet Deng, by by polymerize obtain polymer, crystallization nucleating agent and other additives stirring after, using extruder 180 DEG C~ Melting mixing is carried out at 280 DEG C, thus can obtain the polypropene composition of the present invention.About crystallization nucleating agent or other additives Addition, be to be removed, after drying steps by polymerization, residual monomer, linked extruder can be used to carry out.In addition, In the present invention, so-called masterbatch can be mixed in acrylic resin in sheet forming, which is to crystallize into high concentration Core agent and polypropylene carry out melting kneading and obtain.

The manufacturing method ＞ of ＜ polypropylene film-making materials

The polypropylene film-making material of the present invention preferably manufactures by the following method：Manufacture includes polypropene composition of the present invention Do not extend sheet material, and this is not extended into sheet material and carries out twin shaft extension.

Well known method can be used to carry out for the manufacturing step and twin shaft extension step for not extending sheet material.

Not extending sheet material can be the individual layer comprising a kind of polypropene composition or two or more Polypropylene compositions are laminated The multilayer of nitride layer.

Forming temperature when carrying out the extension of above-mentioned twin shaft is preferably 140 DEG C~170 DEG C, more preferably 150 DEG C~165 DEG C, Especially preferably 155 DEG C~160 DEG C.If the forming temperature is more than the lower limiting value of above range, it is easy to get excellent Thickness precision, if it is upper limit value hereinafter, being then difficult to generate the bad orders such as gonorrhoea.

Forming speed is preferably more than 20%/second, more preferably 50%/second~300%/second, especially preferably 100%/ Second~200%/second.If the forming speed for above range lower limiting value more than and upper limit value hereinafter, if be easy to get it is excellent Thickness precision and it is preferred that.In addition, the forming speed of such as every 1 second is 100%, refer to that the length of former sheet material after 1 second becomes 2 Times.The upper limit of forming speed in reality is or so 500%/second, below preferably 400%/second.

The extension ratio of the preferred MD directions of extension ratio (also referred to as longitudinal direction) and TD directions (also referred to as transverse direction) is 3 Times~6 times, more preferably 3 times~5 times, especially preferably 3 times~4 times.If the extension ratio is the lower limiting value of above range More than, then high rigidity is easy to get, if it is upper limit value hereinafter, then easily being obtained when secondary forming product are made to this sheet material figuration Obtain good formability.

The MD/TD of the ratio of the extension ratio in expression MD directions and the extension ratio in TD directions, preferably 1/2~2/1, it is more excellent It is selected as 2/3~3/2, most preferably 1/1.

＜ includes the manufacturing method ＞ of the secondary forming body of polypropylene film-making material

The polypropylene film-making material (twin shaft extension sheet material) of the present invention can by well known vacuum forming, the empty forming of vacuum pressure, The thermo shaping methods such as hot plate forming, are easily processed into container or pallet.Through secondary forming formed products can be used as packed meal container, Dish pallet, heat-insulated container etc..

[embodiment]

The present invention will be described in more detail for embodiment used below, but the present invention is not limited to these embodiments.

＜ measuring devices ＞

[ethylene contents in copolymer]

About the ethylene contents in copolymer, to being dissolved in 1, the sample of the in the mixed solvent of 2,4- trichloro-benzenes/deuterate benzene, Using Japan Electronics Corporation manufacture JNM LA-400 (¹³C resonant frequency 100MHz), according to utilization¹³The value that C-NMR methods measure It calculates.

[mist degree]

The mist degree of polypropylene film-making material be using haze meter (in village Co., Ltd. of color technical research institute manufacture, HM- 150) it, is measured using the above method.

[Production Example 1：The preparation (1) of solid catalyst component]

The preparation method of the embodiment record of No. 2011-500907 is disclosed according to Japanese patent application, prepares solid catalysis Agent ingredient.Specifically as described below：

In the four round flask of the 500mL rinsed through nitrogen, the TiCl of 250mL is imported at 0 DEG C₄.It stirs on one side, one The side fine spherical MgCl of addition 10.0g₂·1.8C₂H₅OH (according to USP-4, method that 399,054 embodiment 2 is recorded, but with 3000rpm is operated and is manufactured instead of 10000rpm) and 9.1 mMs of 2,3- (diisopropyl) diethyl succinates.Make temperature Degree rises to 100 DEG C, and is kept for 120 minutes.Then, stop stirring, precipitate solid product, and supernatant is sucked out.Then, weight Multiple less than 2 times operations：Add the new TiCl of 250mL₄, mixture is made to be reacted 60 minutes at 120 DEG C, and supernatant is sucked out.60 DEG C solid is cleaned 6 times with anhydrous hexane (6 × 100mL), obtain solid catalyst (1).

[Production Example 2：The manufacture of polypropene composition B]

Make above-mentioned solid catalyst (1) and triethyl aluminum (TEAL) and diisopropyl dimethoxy silane (DIPMS) according to Following amount contacts 24 minutes at 12 DEG C：The mass ratio that TEAL is 11, TEAL/DIPMS relative to the mass ratio of solid catalyst It is 3.The caltalyst of gained is tied up in liquid propene and is kept for 5 minutes at 20 DEG C under suspended state, thus carries out prepolymerization, Obtain prepolymer (1).

The prepolymer (1) of gained is imported into polymer reactor, supply propylene supplies a small amount of second as monomer Alkene and the hydrogen as molecular weight regulator so that the density of hydrogen in polymer reactor is 0.132mol%, ethylene concentration is 0.033mol%.Polymerization temperature is adjusted to 70 DEG C, polymerization pressure is adjusted to 30bar, thus synthesizes the propylene containing ethylene Based polymer.

Relative to 100 mass parts of acrylic polymer containing ethylene of gained, the nonoses alcohol of content shown in table is added Be the nucleating agent Millad NX8000 of manufacture (Japanese Milliken Co.) as crystallization nucleating agent, while allocate antioxidant (bar The B225 of Si Fu companies manufacture) 0.05 mass parts of 0.24 mass parts and neutralizer (calcium stearate), using extruder at 230 DEG C It carries out melting and is kneaded acquisition polypropene composition B.

By ethylene contents, Mw/Mn, the dimethylbenzene of the acrylic polymer containing ethylene in the polypropene composition of gained The mmmm of insoluble component amount and dimethylbenzene insoluble component, the MFR of polypropene composition, crystallization nucleating agent content and t_1/2Value It is shown in table 1, table 2 (same as below).

[Production Example 3：The manufacture of polypropene composition C-1-1]

In Production Example 2, the density of hydrogen in polymer reactor is changed to 0.067mol%.In addition to this, with system The identical mode of example 2 is made, synthesizes the acrylic polymer containing ethylene, and obtains polypropene composition C-1-1.

[Production Example 4：The manufacture of polypropene composition C-1-2]

In Production Example 3, the additive amount of crystallization nucleating agent is changed, in addition to this, obtains polypropylene group in an identical manner Close object C-1-2.

[Production Example 5：The manufacture of polypropene composition C-2]

In Production Example 3, the density of hydrogen in polymer reactor is set as 0.069mol%, is set as ethylene concentration 0.083mol%, and the ethylene contents of composition are changed, in addition to this, polypropene composition C-2 is obtained in an identical manner.

[Production Example 6：The manufacture of polypropene composition C-3-1]

In Production Example 3, the density of hydrogen in polymer reactor is set as 0.070mol%, is set as ethylene concentration 0.118mol%, and the ethylene contents of composition and the additive amount of crystallization nucleating agent are changed, in addition to this, in an identical manner Obtain polypropene composition C-3-1.

[Production Example 7：The manufacture of polypropene composition C-3-3]

In Production Example 6, the additive amount of crystallization nucleating agent is changed, in addition to this, obtains polypropylene group in an identical manner Close object C-3-3.

[comparison manufacturing example 8：The manufacture of polypropene composition C-3-4]

In Production Example 6, crystallization nucleating agent is not added, in addition to this, obtains polypropene composition C- in an identical manner 3-4。

[comparison manufacturing example 9：The manufacture of polypropene composition C-3-5]

In Production Example 6, the additive amount of crystallization nucleating agent is changed, in addition to this, obtains polypropylene group in an identical manner Close object C-3-5.

[Production Example 10：The manufacture of polypropene composition C-4]

In Production Example 3, the density of hydrogen in polymer reactor is set as 0.072mol%, is set as ethylene concentration 0.189mol%, and the ethylene contents of composition and the additive amount of crystallization nucleating agent are changed, in addition to this, in an identical manner Obtain polypropene composition C-4.

[comparison manufacturing example 11：The manufacture of polypropene composition C-5]

In Production Example 3, the density of hydrogen in polymer reactor is set as 0.076mol%, is set as ethylene concentration 0.272mol%, and the ethylene contents of composition and the additive amount of crystallization nucleating agent are changed, in addition to this, in an identical manner Obtain polypropene composition C-5.

[Production Example 12：The preparation (2) of solid catalyst component]

According to the method that the embodiment 1 of No. 674991 bulletin of European Patent is recorded, solid catalyst (2) is prepared.This is solid Body catalyst is the method recorded by above-mentioned patent gazette, in MgCl₂On hold Ti and the adjacent benzene two as internal donor Solid catalyst obtained by diisobutyl formate.

[comparison manufacturing example 13：The manufacture of polypropene composition D]

Make above-mentioned solid catalyst (2) and TEAL and Cyclohexyl Methyl Dimethoxysilane (CHMMS) according to following amount It is contacted 5 minutes at -5 DEG C：TEAL is 0.02 relative to the molar ratio that the weight ratio of solid catalyst is 8, CHMMS/TEAL.By institute The caltalyst obtained is tied up in liquid propene and is kept for 5 minutes at 20 DEG C under suspended state, thus carries out prepolymerization, obtains pre-polymerization Object (2).

In Production Example 3, prepolymer (1) is changed to prepolymer (2), the density of hydrogen in polymer reactor is set as 0.042mol%, and the additive amount of crystallization nucleating agent is changed, in addition to this, polypropene composition D is obtained in an identical manner.

[comparison manufacturing example 14：The manufacture of polypropene composition A-1]

Above-mentioned prepolymer (1) is imported in polymer reactor, and supplies propylene, while supplies hydrogen and causes polymer reactor Interior density of hydrogen is 0.066mol%, and polymerization temperature is adjusted to 70 DEG C, polymerization pressure is adjusted to 30bar, is thus polymerize Noblen.

In the Noblen of gained, the nonoses alcohol system nucleating agent (above-mentioned NX8000) of content shown in table is added, together When antioxidant and neutralizer are allocated in the same manner as Production Example 2, carry out melting using extruder and be kneaded to obtain polypropene composition A-1。

In table, ethylene contents are 0 to refer to that the polymer in polypropene composition is Noblen.

[comparison manufacturing example 15：The manufacture of polypropene composition A-2]

In Production Example 2, crystallization nucleating agent is not added, in addition to this, obtains polypropene composition A- in an identical manner 2。

[1~example of example 12,14~example of example 22, example 24]

1~example of example 12 is embodiment, and 14~example of example 22, example 24 are comparative examples.

Using the polypropene composition shown in table, twin shaft extension sheet material is manufactured as follows.

First, using T die heads forming machine, (lucky well ironworker company manufacture, multilayer T die heads forming machine, screw diameter are 25mm), under conditions of roll temperature is 30 DEG C (uses air knife), 10cm × 10cm is obtained, specific thickness does not extend sheet material.

Then, using twin shaft extension apparatus (manufacture of Bruckner (Bruckner) company, KARO IV), make non-Extendible flake Extend simultaneously towards both direction under material condition shown in table (forming temperature, forming speed, extension ratio), obtain institute in table Show the polypropylene film-making material (twin shaft extension sheet material) of thickness.

The thickness of polypropylene film-making material, thickness precision, tensile modulus of elasticity, face impact strength, mist degree, utilization obtained by measuring The image definition (transparency) that through transmission technique obtains.In addition, measure above-mentioned 160 DEG C when tension test in extension strain and elongation Stress when 200%, according to its measured value according to following benchmark evaluations carry out hot forming when easy hot-forming property (secondary forming property). Load deformation temperature as described above, is evaluated using container obtained by twin shaft extension sheet material is carried out hot forming.By it Result be shown in table 1, table 2 (same as below).

(evaluation of easy hot-forming property)

〇：Stress is less than 10MPa when extension strain value is more than 200% and elongation 200%

×：Stress is more than 10MPa when extension strain value is less than 200% or extends 200%

[example 13]

Example 13 is embodiment.

In a manner of same as Example 1, thickness of the manufacture comprising polypropene composition B is 260 μ ms 2 (surface layer and backing layer) Do not extend sheet material.In addition, in a manner of same as Example 4, thickness of the manufacture comprising polypropene composition C-3-1 for 2080 μm not Extend sheet material (middle layer).Using above-mentioned twin shaft extension apparatus, the sandwich for obtaining the above-mentioned layer of overlapping, the condition shown in table Extend simultaneously towards both direction under (forming temperature, forming speed, extension ratio), obtain the polypropylene film-making material for including three layers (twin shaft extension sheet material).

[example 23]

Example 23 is comparative example.

Using including extruder that 3 screw diameters are 25mm, be provided with the multilayer tablets of the T die heads that can carry out 3 layer stackups Material forming machine (manufacture of thermoplastic materials Industrial Co., Ltd), to make sheet material.More specifically, using all 3 extruders, make to gather Propylene resin C-3-1 is in 230 DEG C of meltings.The T die head temperatures that width is 300mm are set as 230 DEG C, make sheet material two sides and metal The circumferential surface contiguity of roller, thus cools down sheet material, obtains the sheet material that thickness is 210 μm.

As shown in table 1, table 2, in 1~example of example 13, the image clearly that mist degree is low, is obtained using through transmission technique is obtained Degree is high and the transparency is excellent, and tensile modulus of elasticity is high and excellent rigidity, at the same the face impact strength at -30 DEG C it is high and low High-impact under temperature also excellent polypropylene film-making material.In addition, these polypropylene film-making materials are that twin shaft extends to easy two The sheet material of the sheet thickness of secondary forming, thickness accuracy value is small and uniform extensibility is excellent, while is stretched in tension test at 160 DEG C Stress is good when long strain and elongation 200%, and easy hot-forming property (secondary forming property) is excellent.In addition, poly- third by 1~example of example 13 Alkene film-making material carries out secondary forming body (container) obtained by hot forming, excellent heat resistance.

In addition, the polypropylene film-making material of example 24 is since thickness to be obtained is more than 500 μm of sheet material, when twin shaft extends The collet clamped sheet material and kept comes off, and can not carry out twin shaft extension to the end.

Claims (7)

1. a kind of polypropene composition, it is characterised in that：It is described comprising acrylic polymer and crystallization nucleating agent containing ethylene Two when the ethylene contents of acrylic polymer containing ethylene are less than 1 mass %, molecular weight distribution mw/mn is 6~20,25 DEG C Toluene insoluble component amount is more than 96.5 mass % and below 99.5 mass % and the stereoregularity of dimethylbenzene insoluble component Mmmm is 97.5%~99.5%, and the crystallization nucleating agent is relative to 100 mass parts of acrylic polymer containing ethylene To be less than 0.18 mass parts, the melt flow rate (MFR) of the polypropene composition is 1g/10 minutes~15g/10 minutes.

2. polypropene composition according to claim 1, it is characterised in that：Following crystallizations speed of the polypropene composition Spend parameter t_1/2More than 1 second；

Crystallization rate parameter t_1/2：The 1/2 required time of Mixed Growth is reached when crystallizing for 120 DEG C.

3. polypropene composition according to claim 1 or 2, it is characterised in that：The propylene polymerization containing ethylene Object uses the catalyst comprising following compositions, makes propylene and vinyl polymerization and obtains,

(A) contain the electron donor compound selected from magnesium, titanium, halogen and succinate based compound as essential component Solid catalyst；

(B) organo-aluminum compound；With

(C) external electron-donor compound.

4. a kind of polypropylene film-making material, it is characterised in that：It is as the polypropene composition described in any one of claims 1 to 3 The sheet material of composition,

The thickness of the polypropylene film-making material is 100 μm~500 μm,

Thickness precision is less than 12 μm,

Stress is less than 10MPa when extension strain is more than 200% and elongation 200% in tension test at 160 DEG C,

Tensile modulus of elasticity at 23 DEG C is more than 1800MPa,

Face impact strength at -30 DEG C is more than 2J,

Mist degree is less than 2.5%,

It is more than 60% using the image definition that through transmission technique obtains.

5. a kind of manufacturing method of polypropylene film-making material, it is characterised in that：It is the polypropylene system described in for manufacturing claims 4 The method of sheet material,

The manufacturing method of the polypropylene film-making material includes not extending sheet material progress pair by what is be made of the polypropene composition The step of axis extends.

6. the manufacturing method of polypropylene film-making material according to claim 5, it is characterised in that：During twin shaft extension into Shape temperature is 140 DEG C~170 DEG C, and forming speed is the extension ratio difference of 20%/second~400%/second, MD directions and TD directions It is 3 times~6 times.

7. a kind of secondary forming body, it is characterised in that：Polypropylene film-making material described in claim 4 is carried out hot forming to form.