CN1637057A - Propylene resin composition - Google Patents
Propylene resin composition Download PDFInfo
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- CN1637057A CN1637057A CNA2004101028640A CN200410102864A CN1637057A CN 1637057 A CN1637057 A CN 1637057A CN A2004101028640 A CNA2004101028640 A CN A2004101028640A CN 200410102864 A CN200410102864 A CN 200410102864A CN 1637057 A CN1637057 A CN 1637057A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0013—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fillers dispersed in the moulding material, e.g. metal particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/76—Measuring, controlling or regulating
- B29C45/77—Measuring, controlling or regulating of velocity or pressure of moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
- B29K2023/12—PP, i.e. polypropylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
The propylene resin composition comprises a polypropylene resin (PP), an elastomer and an inorganic filler as main constituents. Characteristics of the PP satisfy requirements of >=0.90 infrared absorbance ratio (peak area at 998 cm[-1]/peak area at 973 cm[-1]) and >=10 Q value (Mw/Mn) obtained by GPC (gel permeation chromatography). Characteristics of the propylene resin composition are within the range satisfying formula (1) X {total amount (%) of soft components}<50, formula (2) Y {heat quantity of crystallization (mJ/mg) of rigid components}>95 and formula (3) Y<-2X+230.
Description
The application is based on Japanese patent application No.2003-434877, and this application is incorporated this paper by reference into.
Technical field
The present invention relates to propylene resin composition.Particularly, the present invention relates to polymer alloy, preferably is the material of moulded products used as injection molding, and described goods are for example for having the side filler rod of big length/thickness than (L/t) (as L/t 〉=200).
Though in this manual with the side filler rod be example the present invention will be described describes, the present invention is not limited to this.
Background technology
Because relatively cheap, physical strength of propylene resin composition and excellent in dimensional stability, in light weight and have excellent weather resistance (see also JP-A-09-40952, corresponding to the documents such as JP-A-09-111067, JP-2002-249635A of Japanese Patent No.3304719), propylene resin composition (matrix material) is widely used as the material that injection molding is above-mentioned side filler rod, and this acrylic resin comprises polypropylene (PP) and joins ethene-alpha-olefin copolymer (EOR) among the PP.
Owing to consider to need material to have high flowability from the angle of production efficiency, in injection molding material, often use the prescription of high workability.
On the other hand, if injection molding material is made with high workability, the trend that produces flash in moulded products is just arranged.Making under the situation of side filler rod that injection molded article for example has big L/t ratio, this trend is remarkable.Its reason is as follows: if L/t is too high, then the injection pressure with the material injection need uprise (being not less than 40MPa with regard to maximum in mold pressure).The result is to be easy to generate the slit under this injection pressure between the mold separation face.
Therefore, need produce the material of flash hardly,, or it be carried out easily so that no longer need the operation of flash.
Known to the inventor, still there is not technology to relate to the propylene resin composition that on the formed material surface, produces flash hardly.
Summary of the invention
In this case, the purpose of this invention is to provide a kind of novel propylene resin composition, when this propylene resin composition is used as injecting forming material, produce flash hardly.
Based on following formation, the invention solves the problems referred to above.
A kind of propylene resin composition, it comprises PP, elastomerics and mineral filler as main ingredient, or comprises PP and mineral filler as main ingredient, and the feature of wherein said PP satisfies one of following two required conditions or satisfies simultaneously, and promptly infrared absorption is than (998cm
-1Peak area and 973cm
-1The ratio of peak area) be not less than 0.90, the Q value (Mw/Mn) that records by GPC is not less than 10; And described propylene resin composition has and is positioned at the eigenwert that satisfies with the X-Y scope of lower inequality (1), (2) and (3):
(1)X＜50，
(2) Y＞95 and
(3)Y＜-2X+2?30
Wherein X is the total amount (%) of the soft component (soft component) that comprises in the propylene resin composition, and Y is the amount (mJ/mg) of the heat of crystallization of the hard component (hard component) that comprises in the propylene resin composition.
The propylene resin composition that satisfies above-mentioned condition when use is during as injecting forming material, even under with the situation of this material injection molding for long moulded products (as the side filler rod), the generation of flash is sharply reduced, and this will describe among the embodiment hereinafter.Thereby the production efficiency of injection molded article is improved on the whole, does not need injection molded article is gone the flash operation because it makes, or makes this processing ease carry out.
Preferably, the propylene resin composition with above-mentioned formation comprises the PP of 50 quality % to 90 quality %, the mineral filler of 0 quality % to the elastomerics of 45 quality % and 1 quality % to 25 quality %.This is the prescription that is used to prevent to produce flash on injection molded article.
As elastomerics, use EOR or styrenic thermoplastic elastomer (vinylbenzene TPE) usually.
Consider that from forming process, dimensional stability equal angles the MFR of preferred elastomer (230 ℃ and 21.2N) is in 0.5g/10 minute to 45g/10 minute scope.
As mineral filler, preferably use talcum.The talcum low price, and can reduce coefficient of linear expansion.
In the olefin resin composition forming process that will have above-mentioned formation is to have to be not less than 200 length/thickness than (L/t) with when being not less than the molded article of 40Mpa maximum in mold pressure, also can reduce the generation of flash.
Preferably, in the resin combination that mainly comprises three kinds of components (being PP, elastomerics and talcum), shown in the following expression, its crystallization inhibition degree is lower than 35mJ/mg.
Crystallization inhibition degree is defined as follows:
(amount of the heat of crystallization of the hard component that in PP/ talcum two component resin compositions, comprises)-(amount of the heat of crystallization of the hard component that in PP/ elastomerics/talcum three component resin compositions, comprises).
Because PP crystallization inhibition degree is low, can reduce the generation of flash.
In three component resin compositions,, use EOR or styrenic thermoplastic elastomer usually as elastomerics.
As mentioned above, according to the preparation of the of the present invention third rare resin combination by following form: elastomerics and mineral filler is mixed with specific PP so that the relation of the amount (X) of amount of the heat of crystallization of hard component (Y) and specific soft component is in the specified range.Therefore, as will reducing the generation of flash described in following examples, making does not need flash operation or feasible this (easily) simple to operate.
Description of drawings
Figure 1A and 1B are the figure of flash detection method among explanation the present invention.
Fig. 2 is the figure with plot point, is illustrated in each embodiment and the comparative example relation of the amount (Y) of the heat of crystallization of the hard component that comprises in amount of the soft component that comprises in the propylene resin composition of the present invention (X) and the described propylene resin composition.
Embodiment
Below will on the basis of embodiment of the present invention, describe the present invention in detail.Incidentally, unless otherwise indicated, functional quality unit is as mixed unit.That is " % " expression " quality % ".
(1) propylene resin composition according to the present invention comprises PP, elastomerics and mineral filler as main ingredient, or comprises PP and mineral filler as main ingredient.
(I) term " PP " not only comprises crystalline propylene homopolymer, and comprises propylene-ethylene copolymers that contains small amount of ethylene and the propylene-ethylene block copolymer that contains crystalline ethylene.For example, when propylene and ethylene copolymer, the content of ethene is chosen as and is not higher than 40%, preferably is not higher than 30%, further preferably is not higher than 10%.
Incidentally, in this manual, specify as follows to the eigenwert of PP and propylene resin composition;
(i) crystallinity index of PP
The infrared absorption that will measure by Infrared spectroscopy is than (998cm
-1Peak area and 973cm
-1The ratio of peak area) as crystallinity index.
Infrared spectroscopy is carried out under following measuring condition by Fourier transform infrared spectroscopy (FI-IR): resolving power is 4cm
-1And quantity survey (quantity survey) is 100 times.
Each peak area is defined as follows: at wave number 973cm
-1The place peak area and at wave number 998cm
-1The peak area at place is regarded as amorphous regions and crystal region respectively.
Use Perkinelmer Inc. (PerkinElmer, Inc.) analytical instrument of Sheng Chaning " Spectrum one " following in the embodiment that is described.
The (ii) molecular weight distribution of PP
As molecular weight distribution, this value is the weight-average molecular weight (Mw) that measures by gel permeation chromatography (GPC) method and the ratio of number-average molecular weight (Mn) with Q value (Mw/Mn).The used condition of GPC method is as follows: eluent is an orthodichlorobenzene, and temperature is 140 ℃.
In the following analytical instrument " 150-C plus " of using in the embodiment that is described Waters (WatersCorporation) to produce.
(iii) the hard group component of propylene resin composition and the total amount of soft component
Relaxation curve according to obtaining by NMR (nucleus magnetic resonance) pulse method is divided into three components with each composition, that is, and and hard component, intermediate component and soft component.Calculate the amount of each component with the amount of each component and the ratio of total composition.The used condition of pulse method is as follows: temperature is 25 ℃, and the time is 500 μ s.Incidentally, the amount of soft component is the summation of the amount of the amount of soft component and intermediate component.
At the following measuring apparatus " JNM-MV25 " that uses JEOL to produce in the embodiment that is described.
The (iv) amount and the temperature of propylene resin composition/hard component crystalline heat of crystallization
Use differential scanning calorimeter (DSC).Condition is as follows: in nitrogen environment, heating rate is 10 ℃/minute, and rate of cooling is 10 ℃/minute.Incidentally, the amount of hard component heat of crystallization is calculated according to following expression: 100Q/P, and wherein Q (mJ/mg) is the amount of the heat of crystallization of propylene resin composition, P (%) is the amount of hard component.
At the following DSC " DSC22C " that uses NSK Electronics Co., Ltd. (Seiko Instruments Inc.) to produce in the embodiment that is described.
(v) melt flow rate (MFR) (MFR)
Under the condition of 230 ℃ and 21.2N, measure MFR according to JIS K 7210 (ISO 1133).
(vi) elastic bending modulus
Is that 23 ℃, crooked speed are that 2mm/ minute and inner-support distance are for measuring the elastic bending modulus under the condition of 64mm according to JIS K 7171 (ISO 178) in temperature.
In the present invention, PP satisfies following feature.Though preferably satisfy the condition of infrared absorption ratio and Q value simultaneously, must not satisfy these two conditions simultaneously.Even, also can obtain effect of the present invention satisfying under the situation of one of them condition.
(a) select infrared absorption than (998cm
-1/ 973cm
-1) be not less than 0.90, preferably it is not less than 0.94.
Infrared absorption is than being the crystallinity index of PP.Along with degree of crystallinity increases, when injection molding, PP at high temperature begins earlier to solidify.The result is to expect that the generation of flash will reduce.Though the upper limit to the infrared absorption ratio has no particular limits, the upper limit of the infrared absorption ratio of commercially available PP is usually in 0.88 to 0.94 scope.
(b) the Q value of selecting to obtain by the GPC method (Mw/Mn) is not less than 10, preferably is not less than 15.
The Q value is the index of molecular weight distribution.Along with the Q value increases, the width of molecular weight distribution increases.Along with the increase of molecular weight distribution width, material will be along the direction diffusion perpendicular to material flow direction in the time of can being expected at injection molding.That is, can expect that the generation of flash will reduce.
(II) elastomerics is had no particular limits.For example, can use rubber and/or thermoplastic elastomer (TPE).
As rubber, use EOR usually herein.
EOR is amorphous (amorphous) multipolymer of ethene and alpha-olefin.For alpha-olefin, can use each molecule to have the alpha-olefin of 3 to 12 carbon atoms.For example, can preferably use per molecule to have the alpha-olefin of 3 to 8 carbon atoms, as propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene etc.
Though the alpha-olefin content to EOR has no particular limits, alpha-olefin content is chosen as 10% to 40% (preferred 15% to 35%).If alpha-olefin content very little, then the noncrystalline degree of EOR becomes too low (that is, it is too high that the degree of crystallinity of EOR becomes), to such an extent as to coefficient of linear expansion shows the trend of increase.If opposite, alpha-olefin content is too big, and then the noncrystalline degree of EOR becomes too high (that is, it is too low that the degree of crystallinity of EOR becomes), to such an extent as to be easy to generate the problem of appearance.
As TPE, can preferably use vinylbenzene TPE (as SEBS, SIS, SBS etc.).
(III) propylene resin composition has to be in and satisfies with the interior eigenwert of the X-Y scope of lower inequality (1), (2) and (3):
(1) X＜50 (preferred X＜40),
(2) Y＞95 (preferred Y＞105) and
(3)Y＜-2X+230
Wherein X is the total amount (%) of the soft component that comprises in the described propylene resin composition, and Y is the amount (mJ/mg) of the heat of crystallization of the hard component that comprises in the described propylene resin composition.
In the above description, the lower limit to X (total amount of soft component) has no particular limits.When use comprised the commercially available high-crystallinity PP of 90% homopolymerization PP, the lower limit of X was usually in 7% to 8% scope.
The upper limit to Y (amount of the heat of crystallization of hard component) has no particular limits, because the generation of flash reduces with the increase of Y.Inequality (3) shows that apparently the upper limit of Y is less than 230.
(IV) in the above description, if propylene resin composition has the inequality (1) that is in satisfied (III), the interior eigenwert of X-Y scope of (2) and (3), then propylene resin composition is had no particular limits.
Each component in the resin combination is different and different with molecular weight distribution (Q value) according to the crystallinity index of PP, and is further different with grade and different according to elastomeric kind.Usually, resin combination comprises the PP of 50% to 90% (preferred 55% to 77%), the mineral filler of the elastomerics and 1% to 25% of 0% to 45% (preferred 0% to 35%) (preferred 5% to 15%).
In the above description, if the amount of PP is too little, then the quantitative change of elastomeric component gets too greatly, is easy to generate flash, the mobile reduction and trend that material is clamminess easily to such an extent as to exist.
If the amount of PP is too big, then get too smallly relatively as the quantitative change of the EOR of elastomeric component, to such an extent as to almost be difficult to obtain required shock absorption feature, and make elastic bending modulus too high (as 1500MPa or higher).
That is,, then be used for the side filler rod feature variation of car body curved surface if this resin combination is used for the side filler rod, and the coefficient of linear expansion of side filler rod that undesirable change takes place is big.
Incidentally, as mineral filler, also can use lime carbonate, mica etc.As mineral filler, use widely used talcum in propylene resin composition usually.The steatitic mean particle size is chosen as 1 μ m in 10 mu m ranges, and preferred 3 μ m are to 6 mu m ranges.Incidentally, mean particle size is measured by laser diffractometry.
If the talcum amount of sneaking into is too big, then the hardness of injection molded article becomes too high.If the steatitic mean particle size is greater than 10 μ m, then the coefficient of linear expansion of injection molded article becomes too big, to such an extent as to dimensional stability reduces.
(V) when resin combination be to be that PP, EOR and steatitic three component resin compositions are when providing mainly to contain three kinds of components, preferably be lower than 35mJ/mg by the resin combination crystallization inhibition degree shown in the expression formula hereinafter, more preferably less than 20mJ/mg, further preferably be lower than 15mJ/mg.
Crystallization inhibition degree is defined as follows:
(amount of the heat of crystallization of the hard component that in PP/ talcum two component resin compositions, comprises)-(amount of the heat of crystallization of the hard component that in PP/ elastomerics/talcum three component resin compositions, comprises).
In the situation of PP/ elastomerics/talcum three component resin compositions, elastomerics is above-mentioned EOR or vinylbenzene TPE.
When injection molded article was used as the side filler rod, the elastic bending modulus of moulded products preferably was not higher than 1600MPa, more preferably no higher than 1200MPa.From reducing the angle consideration that flash produces, the MFR of molding resin composition (230 ℃ and 21.2N) preferably was not less than 10g/10 minute, more preferably was not less than 20g/10 minute, further preferably was not less than 30g/10 minute.Incidentally,, significantly produce ripple easily, that is, the problem of moulded products outward appearance takes place easily if the Q value is little and MFR is too low.
(2) common propylene resin composition provides with the form of injecting forming material (pellet); this material is by under the condition in the polymer alloy that talcum and other subsidiary material (as pigment, antioxidant, uv-absorbing agent, photostabilizer, dispersion agent, static inhibitor etc.) is suitably joined PP and EOR, provides by the ordinary method of using tablets press.Pellet material is used to injection molding for long injection molded article, as the side filler rod.
For example, in this case, injection molding condition is as follows: barrel temperature is 190 ℃ to 240 ℃, and mold temperature is 20 ℃ to 50 ℃, and injection pressure is that 40MPa is to 100MPa.
Embodiment
In order to confirm effect of the present invention, embodiment is described below.
According to above measuring eigenwert based on each propylene resin composition of prescription shown in table 1 and the table 2 about the described method of technical term.By tablets press with each propylene resin composition preparation becoming injecting forming material.Injecting forming material is carried out following flash produce test.
Incidentally, as PP and elastomerics, use material respectively with eigenwert shown in table 3 and the table 4.Using mean particle size is that the material of 4 μ m is as talcum.
Use shown in Figure 1A, its vertical view has the former 12 and the flat-die (flat mold) 14 of plate-like cavity 11, under following condition of molding, injection molding is the moulded products (diameter 75mm, thickness 1.5mm) 16 with shape shown in Figure 1B with each material.Incidentally, label 18 expression cast gates, 18A represents the moulding cast gate.
In plate-like cavity 11, radially form the degree of depth and be marked in groove (10mm is wide) on the periphery.Measure the length of the length of overflow portion 16a in each groove (slit) as flash.
Mold temperature: 220 ℃; Die temperature: 30 ℃; Injection pressure: 15.7MPa; Injection rate: 48mm/s; Follow-up pressure: 3.5MPa.
Assess, so that the flash length in the 20 μ m die gap is able to be identified based on following standard.
Zero ... be not more than 100 μ m; △ ... greater than 100 μ m but be not more than 130 μ m; * ... greater than 130 μ m.
Apparent from table 1 and table 2 and evaluation result shown in Figure 2, among each embodiment within the scope of the present invention, the length of flash is little,, does not almost produce flash that is.
Table 1
| Composition/prescription | Comparative example 1 | Embodiment 1 | Embodiment 2 | Comparative example 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 3 | ||
| ??PP-1 | ??55.0 | ????70.0 | |||||||||
| ??PP-2 | ??55.0 | ||||||||||
| ??PP-3 | ??55.0 | ||||||||||
| ??PP-4 | ??55.0 | ||||||||||
| ??PP-5 | ??65.0 | ??60.0 | ??50.0 | ??40.0 | |||||||
| Elastomerics-1 | ??35.0 | ??35.0 | ??35.0 | ????20.0 | ??35.0 | ||||||
| Elastomerics-2 | ??25.0 | ??30.0 | ??40.0 | ??50.0 | |||||||
| Talcum (mean particle size: 4.0 μ m) | ??10.0 | ??10.0 | ??10.0 | ????10.0 | ??10.0 | ??10.0 | ??10.0 | ??10.0 | ??10.0 | ||
| Composition/moulded products feature | MFR (g/10 minute) | ??14.1 | ??11.2 | ??11.8 | ????19.6 | ??5.8 | ??37.1 | ??30.1 | ??21.1 | ??12.2 | |
| Elastic bending modulus (MPa) | ??763 | ??873 | ??1121 | ????1049 | ??1010 | ??1581 | ??1451 | ??1239 | ??101?9 | ||
| The amount of heat of crystallization (mJ/mg) | ??45.7 | ??44.3 | ??57.8 | ????62.3 | ??52.5 | ??69.0 | ??63.2 | ??52.8 | ??37.9 | ||
| The amount of the heat of crystallization of hard component (mJ/mg) Y | ??125.2 | ??104.0 | ??131.4 | ????141.0 | ??126.8 | ??117.7 | ??114.1 | ??109.1 | ??90.7 | ||
| The total amount of hard component (quality %) | ??36.5 | ??42.6 | ??44.0 | ????44.3 | ??41.4 | ??58.6 | ??55.4 | ??49.1 | ??43.7 | ||
| The total amount of soft component (quality %) X | ??53.5 | ??47.4 | ??46.0 | ????45.7 | ??48.6 | ??31.4 | ??34.6 | ??40.9 | ??46.3 | ||
| Crystallization inhibition degree (Y 0-Y) | ??- | ??- | ??- | ????- | ??- | ??10.6 | ??14.2 | ??19.2 | ??37.6 | ||
| Flash length (μ m) | Slit 20 μ m | ??130 ??× | ??115 ??△ | ??76 ??○ | ????169 ????× | ??119 ??△ | ??85 ??○ | ??84 ??○ | ??120 ??△ | ??210 ??× | |
Table 2
| Composition/prescription | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | ||
| ??PP-1 | ||||||||||
| ??PP-2 | ||||||||||
| ??PP-3 | ||||||||||
| ??PP-4 | ||||||||||
| ??PP-5 | ??60.0 | ??50.0 | ??60.0 | ??60.0 | ??60.0 | ??60.0 | ??60.0 | ????90 | ||
| Elastomerics-1 | ??30.0 | |||||||||
| Elastomerics-2 | ??30.0 | |||||||||
| Elastomerics-3 | ??30.0 | |||||||||
| Elastomerics-4 | ??30.0 | |||||||||
| Elastomerics-5 | ??30.0 | |||||||||
| Elastomerics-6 | ??30.0 | |||||||||
| Elastomerics-7 | ??30.0 | |||||||||
| Talcum (mean particle size: 4.0 μ m) | ??10.0 | ??20.0 | ??10.0 | ??10.0 | ??10.0 | ??10.0 | ??10.0 | ????10.0 | ||
| Composition/moulded products feature | MFR (g/10 minute) | ??40.6 | ??20.4 | ??54.6 | ??70.4 | ??39.2 | ??32.7 | ??56.5 | ????105.8 | |
| Elastic bending modulus (MPa) | ??1463 | ??1721 | ??1460 | ??1452 | ??1497 | ??1387 | ??1166 | ????2384 | ||
| The amount of heat of crystallization (mJ/mg) | ??64.9 | ??53.9 | ??62.3 | ??62.1 | ??61.9 | ??62.4 | ??62.1 | ????97.0 | ||
| The amount of the heat of crystallization of hard component (mJ/mg) Y | ??116.7 | ??113.5 | ??115.8 | ??115.9 | ??109.6 | ??22.4 | ??126.0 | ????128.3(Y 0) | ||
| The total amount of hard component (quality %) | ??55.6 | ??47.5 | ??53.8 | ??53.6 | ??56.5 | ??51.0 | ??49.3 | ????75.6 | ||
| The total amount of soft component (quality %) X | ??34.4 | ??32.5 | ??36.2 | ??36.4 | ??33.5 | ??39.0 | ??40.7 | ????14.4 | ||
| Crystallization inhibition degree (Y 0-Y) | ??11.6 | ??14.8 | ??12.5 | ??12.4 | ??18.7 | ??5.9 | ??2.3 | ????- | ||
| Flash length (μ m) | Slit 20 μ m | ??97 ??○ | ??85 ??○ | ??99 ??○ | ??127 ??△ | ??70 ??○ | ??80 ??○ | ??107 ??△ | ????83 ????○ | |
Table 3
| ????PP | Ethylene content | ????MFR * | Crystallinity index | Molecular weight distribution |
| Weight % | G/10 minute | ????- | ????- | |
| ????PP-1 | ????19.0 | ????30 | ????0.882 | ????8.8 |
| ????PP-2 | ????10.1 | ????28 | ????0.835 | ????16.1 |
| ????PP-3 | ????39.5 | ????32 | ????0.951 | ????15.7 |
| ????PP-4 | ????2.0 | ????10 | ????0.934 | ????9.2 |
| ????PP-5 | ????5.1 | ????110 | ????0.950 | ????11.5 |
*230 ℃ and 21.2N
Table 4
| Elastomerics | Component | Co-monomer content | ????MFR * |
| (alpha-olefin etc.) | G/10 minute | ||
| Elastomerics-1 | ????EPM | Propylene: 24% | ????5.4 |
| Elastomerics-2 | ????0.7 | ||
| Elastomerics-3 | ????8.1 | ||
| Elastomerics-4 | ????40.0 | ||
| Elastomerics-5 | ????EBM | 1-butylene: 20% | ????1.9 |
| Elastomerics-6 | ????EOM | 1-octene: 35% | ????2.0 |
| Elastomerics-7 | ????SEBS | Vinylbenzene: 13% | ????7.0 |
*230 ℃ and 21.2N
Claims (13)
1. a rare resin combination comprises PP and mineral filler as main ingredient, wherein,
Described PP has the feature that satisfies at least one required condition, and required condition is an infrared absorption than being not less than 0.90 and be not less than 10 by the Q value that GPC obtains; And
Described resin combination has to be in and satisfies with the interior eigenwert of the X-Y scope of lower inequality (1), (2) and (3):
(1)X＜50，
(2) Y＞95 and
(3)Y＜-2X+230
Wherein X is the total amount (%) of the soft component that comprises in the described resin combination, and Y is the amount (mJ/mg) of the heat of crystallization of the hard component that comprises in the described resin combination.
2. according to the propylene resin composition of claim 1, wherein said resin combination comprises the mineral filler of 50 quality % to the PP of 90 quality % and 1 quality % to 25 quality %.
3. according to the propylene resin composition of claim 1, wherein said mineral filler is a talcum.
4. one kind is carried out the injection molded article that injection molding is made by the propylene resin composition that claim 1 is limited, and wherein said injection molded article satisfies following relation:
L/t≥200
Wherein L is the length of described injection molded article, and t is the thickness of described injection molded article.
5. an injection moulding method comprises that the propylene resin composition that claim 1 is limited is the step of injection molded article at the condition compacted under that maximum in mold pressure is not less than 40Mpa, and wherein said injection molded article satisfies following relation:
L/t≥200
Wherein L is the length of described injection molded article, and t is the thickness of described injection molded article.
6. a rare resin combination comprises PP, elastomerics and mineral filler as main ingredient, wherein,
PP has the feature that satisfies at least one required condition, and required condition is an infrared absorption than being not less than 0.90 and be not less than 10 by the Q value that GPC obtains; And
Described resin combination has to be in and satisfies with the interior eigenwert of the X-Y scope of lower inequality (1), (2) and (3):
(1)X＜50，
(2) Y＞95 and
(3)Y＜-2X+230
Wherein X is the total amount (%) of the soft component that comprises in the described resin combination, and Y is the amount (mJ/mg) of the heat of crystallization of the hard component that comprises in the described resin combination.
7. according to the propylene resin composition of claim 6, wherein said resin combination comprise 50 quality % to PP, the 0 quality % of 90 quality % to 45 quality % elastomerics and 1 quality % to the mineral filler of 25 quality %.
8. according to the propylene resin composition of claim 6, wherein said mineral filler is a talcum.
9. one kind is carried out the injection molded article that injection molding is made by the propylene resin composition that claim 6 is limited, and wherein said injection molded article satisfies following relation:
L/t≥200
Wherein L is the length of described injection molded article, and t is the thickness of described injection molded article.
10. an injection moulding method comprises that the propylene resin composition that claim 6 is limited is the step of injection molded article at the condition compacted under that maximum in mold pressure is not less than 40MPa, and wherein said injection molded article satisfies following relation:
L/t≥200
Wherein L is the length of described injection molded article, and t is the thickness of described injection molded article.
11. a propylene resin composition, it is to comprise PP, elastomerics and steatitic three component resin compositions basically, and wherein said resin combination satisfies the condition that crystallization inhibition degree is lower than 35mJ/mg.
12. according to the propylene resin composition of claim 11, wherein said elastomerics is EOR.
13. according to the propylene resin composition of claim 11, wherein said elastomerics is vinylbenzene TPE.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003434877 | 2003-12-26 | ||
| JP2003434877A JP2005194297A (en) | 2003-12-26 | 2003-12-26 | Propylene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1637057A true CN1637057A (en) | 2005-07-13 |
| CN1323110C CN1323110C (en) | 2007-06-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004101028640A Expired - Fee Related CN1323110C (en) | 2003-12-26 | 2004-12-24 | Propylene resin composition |
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| Country | Link |
|---|---|
| JP (1) | JP2005194297A (en) |
| CN (1) | CN1323110C (en) |
| DE (1) | DE102004061859B4 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727688A (en) * | 2017-04-14 | 2018-11-02 | 住友化学株式会社 | Propylene resin composition and moulded products |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| BR112013028817A2 (en) * | 2011-05-20 | 2017-01-31 | Procter & Gamble | method for substantially constant low pressure injection molding |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH075668B2 (en) * | 1987-02-04 | 1995-01-25 | チッソ株式会社 | Highly crystalline polypropylene |
| JPH0733920Y2 (en) * | 1990-10-23 | 1995-08-02 | 海洋工業株式会社 | Pumping equipment |
| JP3732623B2 (en) * | 1996-08-16 | 2006-01-05 | 出光興産株式会社 | Polypropylene resin and polypropylene resin composition |
| EP0916701B1 (en) * | 1997-04-24 | 2004-02-25 | Mitsui Chemicals, Inc. | Crystalline polypropylene resin composition |
| US6576699B2 (en) * | 1997-09-03 | 2003-06-10 | Toyoda Gosei Co., Ltd. | Damping resin composition and molded article using the same |
| JP2001106841A (en) * | 1999-10-06 | 2001-04-17 | Mitsui Chemicals Inc | Syndiotactic polypropylene based composition |
| US6300419B1 (en) * | 1999-12-08 | 2001-10-09 | The Dow Chemical Company | Propylene polymer composition |
| JP4233240B2 (en) * | 2000-06-22 | 2009-03-04 | 三井化学株式会社 | Injection foam molding method, and injection molding machine and resin composition suitable therefor |
| US6838510B2 (en) * | 2001-05-24 | 2005-01-04 | Mitsui Chemicals, Inc. | Resin composition for automotive exterior parts |
| JP2003226853A (en) * | 2002-02-05 | 2003-08-15 | Sumitomo Chem Co Ltd | Adhesive |
-
2003
- 2003-12-26 JP JP2003434877A patent/JP2005194297A/en active Pending
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- 2004-12-22 DE DE102004061859A patent/DE102004061859B4/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108727688A (en) * | 2017-04-14 | 2018-11-02 | 住友化学株式会社 | Propylene resin composition and moulded products |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005194297A (en) | 2005-07-21 |
| CN1323110C (en) | 2007-06-27 |
| DE102004061859A1 (en) | 2005-07-28 |
| DE102004061859B4 (en) | 2009-07-09 |
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