阅读说明：本技术 丙烯树脂组合物以及成型体 (Propylene resin composition and molded article ) 是由 袋田裕史 真田敏春 于 2020-03-25 设计创作，主要内容包括：一种丙烯树脂组合物,所述丙烯树脂组合物包含：30重量份～65重量份的丙烯类聚合物(A)；10重量份～40重量份的乙烯-α-烯烃无规共聚物(B)；10重量份～40重量份的填充材料(C)；和0.1重量份～10重量份的乙烯-α-烯烃嵌段共聚物(D),其中,成分A～D的含量的合计为100重量份,在20℃下成分D的二甲苯可溶成分为70重量％以下,并且成分D的密度为0.865g/cm～(3)～0.867g/cm～(3)。(A propylene resin composition comprising: 30 to 65 parts by weight of a propylene polymer (A); 10 to 40 parts by weight of an ethylene-alpha-olefin random copolymer (B); 10 to 40 parts by weight of a filler (C); and 0.1 to 10 parts by weight of an ethylene-alpha-olefin block copolymer (D), wherein the total content of the components A to D is 100 parts by weight, the xylene-soluble component of the component D is 70% by weight or less at 20 ℃, and the density of the component D is 0.865g/cm 3 ～0.867g/cm 3 。)

1. A propylene resin composition comprising:

30 to 65 parts by weight of a propylene polymer (A);

10 to 40 parts by weight of an ethylene-alpha-olefin random copolymer (B);

10 to 40 parts by weight of a filler (C); and

0.1 to 10 parts by weight of an ethylene-alpha-olefin block copolymer (D) wherein,

the total content of the components A to D is 100 parts by weight,

the xylene-soluble component of the component D is 70 wt% or less at 20 ℃ and

the density of the component D is 0.865g/cm³～0.867g/cm³。

2. The propylene resin composition according to claim 1, wherein the component D has a melt flow rate (190 ℃ C., 2.16kg load) of 0.5g/10 min to 10g/10 min.

3. The propylene resin composition according to claim 1 or 2, wherein the propylene resin composition further comprises component E:

0.1 to 5 parts by weight, shear rate 61 seconds^-1The extrusion swell ratio and the shear rate were 6080 seconds^-1The absolute value of the difference in the die swell ratio is 0.35 or less.

4. The propylene resin composition according to claim 3, wherein the crystallization time of the component E is 150 seconds or less at 135 ℃.

5. A molded article comprising the propylene resin composition according to any one of claims 1 to 4.

Technical Field

The present invention relates to a propylene resin composition and a molded article.

Background

Molded articles comprising a propylene resin composition are used for automobile materials, household electric appliances, and the like, and for example, patent document 1 describes a polypropylene resin composition comprising crystalline polypropylene, a long-chain branched propylene-based polymer, a thermoplastic elastomer, and an inorganic filler.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2011-

Disclosure of Invention

Problems to be solved by the invention

In recent years, molded articles used for automobile materials and the like are required to have high dimensional stability.

Accordingly, an object of the present invention is to provide a propylene resin composition capable of producing a molded article having excellent dimensional stability. It is another object of the present invention to provide a molded article having excellent dimensional stability.

Means for solving the problems

The present invention relates to the following, but is not limited thereto.

[ invention 1]

A propylene resin composition comprising:

30 to 65 parts by weight of a propylene polymer (A);

10 to 40 parts by weight of an ethylene-alpha-olefin random copolymer (B);

10 to 40 parts by weight of a filler (C); and

0.1 to 10 parts by weight of an ethylene-alpha-olefin block copolymer (D) wherein,

the total content of the components A to D is 100 parts by weight,

the xylene-soluble component of the component D is 70 wt% or less at 20 ℃ and

the density of the component D is 0.865g/cm³～0.867g/cm³。

[ invention 2]

The propylene resin composition according to invention 1, wherein the component D has a melt flow rate (190 ℃ C., 2.16kg load) of 0.5g/10 min to 10g/10 min.

[ invention 3]

The propylene resin composition according to invention 1 or 2, wherein the propylene resin composition further comprises component E:

0.1 to 5 parts by weight, shear rate 61 seconds ^-1The extrusion swell ratio and the shear rate were 6080 seconds^-1The absolute value of the difference in the die swell ratio is 0.35 or less.

[ invention 4]

The propylene resin composition according to invention 3, wherein the crystallization time of component E is 150 seconds or less at 135 ℃.

[ invention 5]

A molded article comprising the propylene resin composition according to any one of the inventions 1 to 4.

Effects of the invention

According to the present invention, a propylene resin composition capable of producing a molded article having a small dimensional stability, specifically, a small linear expansion coefficient can be provided. According to the present invention, a molded article having excellent dimensional stability can be provided.

Drawings

FIG. 1 is a schematic view of an injection-molded body for evaluating a linear expansion coefficient.

Fig. 2 is a schematic view of an injection-molded body for evaluating weld-joint hinge resistance.

Detailed Description

Definition of

In the present specification, the term "propylene resin composition" refers to a composition containing a propylene-based polymer. As will be described in detail hereinafter.

In the present specification, the term "propylene-based polymer" will be described in detail later.

In this specification, the term "α -olefin" refers to an aliphatic unsaturated hydrocarbon having a carbon-carbon unsaturated double bond at the α -position.

In the present specification, the term "ethylene- α -olefin random copolymer" means a random copolymer containing a monomer unit derived from ethylene and a monomer unit derived from an α -olefin of C4 or more (means a number of carbon atoms of 4 or more, and the same applies to other similar expressions), and substantially not containing a monomer unit derived from propylene. As will be described in detail hereinafter.

In the present specification, the term "heterophasic propylene polymeric material" refers to a mixture comprising a polymer I containing 80 wt% or more of monomer units derived from propylene (wherein the total weight of the polymer I is set to 100 wt%), and a polymer II containing monomer units derived from at least one α -olefin selected from the group consisting of ethylene and C4-12 α -olefins, and monomer units derived from propylene.

In the present specification, the term "xylene-insoluble fraction (also referred to as" CXIS fraction ")" means a fraction insoluble in p-xylene contained in a polymer, and means a solid obtained by the following method,

about 2g of the polymer was dissolved in boiling p-xylene for 2 hours to obtain a solution, and then the solution was cooled to 20 ℃ to precipitate solids.

In this specification, the term "xylene-soluble fraction (also referred to as" CXS fraction ")" refers to a fraction of the polymer other than the "CXIS fraction".

In the present specification, the term "filler" is defined in detail later.

In the present specification, the term "ethylene- α -olefin block copolymer" is a block copolymer containing a monomer unit derived from ethylene and a monomer unit derived from an α -olefin of C4 or more, and substantially not containing a monomer unit derived from propylene. As will be described in detail hereinafter.

All numbers disclosed in this specification are approximate values, whether used in association with such words as "about" or "approximately". These values may vary by 1%, 2%, 5%, or sometimes 10% to 20%. In the disclosure with a lower limit of R^LAnd an upper limit R^UIn the case of a numerical range of (a), any numerical value contained in the range is always specifically disclosed. In particular, the following values within the ranges are specifically disclosed. R ═ R^L+k×(R^U-R^L) (wherein k is 1% to 100%Each 1% increase in the range, i.e., k is 1%, 2%, 3%, 4%, 5%, … … 50%, 51%, 52%, … … 95%, 96%, 97%, 98%, 99%, or 100%). In addition, any numerical range defined by the numerical values of the two R described above is also specifically disclosed.

Some embodiments of the present invention are described in detail below. However, the present invention is not limited to the following embodiments. In the present specification, the term "lower limit to upper limit" indicating a numerical range means "not lower than the lower limit but not higher than the upper limit", and the term "upper limit to lower limit" means "not lower than the upper limit but not lower than the lower limit". That is, these descriptions represent numerical ranges including a lower limit and an upper limit.

Propylene resin composition

In the present invention, the "propylene resin composition (hereinafter also simply referred to as a resin composition)" includes a propylene polymer (a), an ethylene- α -olefin random copolymer (B), a filler (C), and an ethylene- α -olefin block copolymer (D), and contains 30 to 65 parts by weight of the component a, 10 to 40 parts by weight of the component B, 10 to 40 parts by weight of the component C, and 0.1 to 10 parts by weight of the component D, based on 100 parts by weight of the total content of the components a to D. By molding such a propylene resin composition, a molded article having excellent dimensional stability can be produced. Further, when the propylene resin composition of the present invention is used, a molded article can be produced by a simple method such as injection molding which is generally employed for producing molded articles for automobiles.

The respective components represented by the "propylene-based polymer (A)" and the like are also simply referred to as "component A" and the like, respectively.

Hereinafter, each component will be described.

Propylene polymer (A)

Component a is a polymer having 50% by weight or more of monomer units derived from propylene. Wherein the shear rate of the component A is 61 seconds^-1The extrusion swell ratio and the shear rate were 6080 seconds^-1The absolute value of the difference between the die swell ratios is greater than 0.35. Examples of component A include: propylene is homogeneousCopolymers, random copolymers of propylene with monomers other than propylene, and heterophasic propylene polymeric materials. The propylene resin composition of the present invention may contain only 1 component a, or may contain 2 or more components a. From the viewpoint of rigidity and impact resistance of the molded article, the component a preferably contains at least one selected from the group consisting of a propylene homopolymer and a heterophasic propylene polymer material.

Propylene homopolymer

When the component A contains a propylene homopolymer, the intrinsic viscosity ([ eta ]) of the propylene homopolymer is preferably 0.10 to 2.00dL/g, more preferably 0.50 to 1.50dL/g, and still more preferably 0.70 to 1.40dL/g, from the viewpoints of the fluidity of the resin composition at the time of melting and the toughness of the molded article.

In the present specification, the intrinsic viscosity (unit: dL/g) is a value measured at a temperature of 135 ℃ by the following method using tetralin as a solvent.

Reduced viscosities were measured at 3 points of concentrations of 0.1g/dL, 0.2g/dL and 0.5g/dL using an Ubbelohde viscometer. Intrinsic viscosity was determined by extrapolation by plotting reduced viscosity versus concentration and extrapolating the concentration to zero. The method of calculating the intrinsic viscosity by extrapolation is described, for example, in "polymer solution, Polymer experiment 11" (published by Kyoho, 1982) on page 491.

The molecular weight distribution (Mw/Mn) of the propylene homopolymer is preferably 3.0 or more, more preferably 4.0 or more. The molecular weight distribution of component A may be 30.0 or less, or may be 25.0 or less. The molecular weight distribution of the component A is preferably 3.0 to 30.0, more preferably 4.0 to 25.0.

In the present specification, the molecular weight distribution refers to a ratio (Mw/Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) calculated using a weight average molecular weight (Mw) and a number average molecular weight (Mn) measured by Gel Permeation Chromatography (GPC) under the following conditions.

The device comprises the following steps: HLC-8121GPC/HT manufactured by Tosoh corporation

Separating the column: GMHHR-H (S) HT 3 manufactured by Tosoh corporation

Measuring temperature: 140 deg.C

Carrier: ortho-dichlorobenzene

Flow rate: 1.0 mL/min

Sample concentration: about 1mg/mL

Sample injection amount: 400 μ L

A detector: differential refraction

The calibration curve making method comprises the following steps: using standard polystyrene

The propylene homopolymer can be produced, for example, by polymerizing propylene using a polymerization catalyst.

Examples of the polymerization catalyst include: a ziegler-type catalyst; a Ziegler-Natta type catalyst; a catalyst comprising a transition metal compound of group 4 of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane; a catalyst comprising a transition metal compound of group 4 of the periodic table having a cyclopentadienyl ring, a compound which forms an ionic complex by reacting with the transition metal compound, and an organoaluminum compound; and a catalyst obtained by modifying inorganic particles (silica, clay mineral, etc.) by supporting thereon a catalyst component (a transition metal compound of group 4 of the periodic table having a cyclopentadienyl ring, a compound forming an ionic complex, an organoaluminum compound, etc.).

Examples of the polymerization catalyst include: catalysts described in Japanese patent laid-open Nos. 61-218606, 5-194685, 7-216017, 9-316147, 10-212319 and 2004-182981.

Further, a polymer obtained by prepolymerizing propylene in the presence of the above polymerization catalyst may be used as the polymerization catalyst.

Examples of the polymerization method include: bulk polymerization, solution polymerization, and gas phase polymerization. The bulk polymerization is a method of polymerizing an olefin in a liquid state at a polymerization temperature as a medium, and the solution polymerization is a method of polymerizing in an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, octane, or the like. In addition, the gas phase polymerization refers to a method of using a gaseous monomer as a medium and polymerizing the gaseous monomer in the medium.

Examples of the polymerization method include: batch, continuous, and combinations thereof.

The polymerization system may be a multistage system in which a plurality of polymerization reaction vessels are connected in series.

From the viewpoint of excellent industrial and economical efficiency, a continuous gas phase polymerization method or a bulk-gas phase polymerization method in which a bulk polymerization method and a gas phase polymerization method are continuously performed is preferable.

Various conditions (polymerization temperature, polymerization pressure, monomer concentration, catalyst input amount, polymerization time, etc.) in the polymerization step can be appropriately determined depending on the molecular structure of the target polymer.

After the polymerization step, the polymer may be dried at a temperature equal to or lower than the temperature at which the polymer melts, if necessary, in order to remove residual solvent contained in the polymer, ultra-low molecular weight oligomers produced as a by-product during production, and the like. Examples of the drying method include: the methods described in Japanese patent laid-open Nos. 55-75410 and 2565753.

Random copolymers of propylene with monomers other than propylene

The random copolymer of propylene and a monomer other than propylene contains a monomer unit derived from propylene and a monomer unit derived from a monomer other than propylene. The random copolymer preferably contains 0.01 to 20% by weight of monomer units derived from a monomer other than propylene, based on the weight of the random copolymer.

Examples of the monomer other than propylene include: ethylene and C4-12 alpha-olefin. Among these, at least one selected from the group consisting of ethylene and C4-10 α -olefins is preferable, at least one selected from the group consisting of ethylene, 1-butene, 1-hexene and 1-octene is more preferable, and at least one selected from the group consisting of ethylene and 1-butene is even more preferable.

Examples of the random copolymer include: propylene-ethylene random copolymer, propylene-1-butene random copolymer, propylene-1-hexene random copolymer, propylene-1-octene random copolymer, propylene-ethylene-1-butene random copolymer, propylene-ethylene-1-hexene random copolymer and propylene-ethylene-1-octene random copolymer.

When the component a contains a random copolymer of propylene and a monomer other than propylene, the intrinsic viscosity ([ η ]) of the random copolymer is preferably 0.10dL/g to 2.00dL/g, more preferably 0.50dL/g to 1.50dL/g, and still more preferably 0.70dL/g to 1.40dL/g, from the viewpoint of fluidity of the resin composition at the time of melting.

The molecular weight distribution (Mw/Mn) of the random polymer is preferably 3.0 or more, more preferably 4.0 or more. The molecular weight distribution of the random polymer may be 30.0 or less, or may be 25.0 or less. The molecular weight distribution of the random polymer is preferably 3.0 to 30.0, more preferably 4.0 to 25.0.

The random copolymer can be produced by polymerizing propylene and a monomer other than propylene in accordance with a polymerization catalyst, a polymerization method, and a polymerization method which can be used for producing the propylene homopolymer.

Heterophasic propylene polymeric material

The heterophasic propylene polymeric material can be produced, for example, by carrying out a first polymerization step to form polymer I and a second polymerization step to form polymer II.

Examples of the polymerization catalyst, the polymerization method and the polymerization method used in these polymerization steps are the same as those described above.

In the heterophasic propylene polymer material, the total amount of polymer I and polymer II contained in the heterophasic propylene polymer material may be 100 wt%, assuming that the total weight of the heterophasic propylene polymer material is 100 wt%.

As mentioned above, polymer I contains more than 80% by weight of monomer units derived from propylene. The polymer I may be, for example, a propylene homopolymer, or may contain monomer units derived from monomers other than propylene. In the case where the polymer I contains a monomer unit derived from a monomer other than propylene, the content of the monomer unit derived from a monomer other than propylene may be, for example, 0.01% by weight or more and less than 20% by weight based on the total weight of the polymer I.

Examples of the monomer other than propylene include: ethylene and alpha-olefins above C4. Among these, at least one selected from the group consisting of ethylene and C4-10 α -olefins is preferable, at least one selected from the group consisting of ethylene, 1-butene, 1-hexene and 1-octene is more preferable, and at least one selected from the group consisting of ethylene and 1-butene is even more preferable.

As the copolymer containing a monomer unit derived from a monomer other than propylene, for example, there can be cited: propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexene copolymers, propylene-1-octene copolymers, propylene-ethylene-1-butene copolymers, propylene-ethylene-1-hexene copolymers and propylene-ethylene-1-octene copolymers.

From the viewpoint of dimensional stability of the molded article, the polymer I is preferably a propylene homopolymer, a propylene-ethylene copolymer, a propylene-1-butene copolymer, or a propylene-ethylene-1-butene copolymer, and more preferably a propylene homopolymer.

The content of polymer I is preferably from 50 to 99 wt.%, more preferably from 60 to 95 wt.%, based on the total weight of the heterophasic propylene polymer material.

As described above, the polymer II contains a monomer unit derived from at least one alpha-olefin selected from the group consisting of ethylene and C4-12 alpha-olefins and a monomer unit derived from propylene. Preferably, the polymer II contains 30% by weight or more of monomer units derived from at least one alpha-olefin selected from the group consisting of ethylene and C4-12 alpha-olefins, and contains monomer units derived from propylene.

In the polymer II, the content of monomer units derived from at least one α -olefin selected from the group consisting of ethylene and α -olefins having from C4 to 12 may be from 30% by weight to 70% by weight, or from 35% by weight to 60% by weight.

In the polymer II, the at least one α -olefin selected from the group consisting of ethylene and α -olefins having from C4 to C12 is preferably at least one selected from the group consisting of ethylene and α -olefins having from C4 to C10, more preferably at least one selected from the group consisting of ethylene, 1-butene, 1-hexene and 1-octene, and even more preferably at least one selected from the group consisting of ethylene and 1-butene.

Examples of polymers II include: propylene-ethylene copolymers, propylene-ethylene-1-butene copolymers, propylene-ethylene-1-hexene copolymers, propylene-ethylene-1-octene copolymers, propylene-ethylene-1-decene copolymers, propylene-1-butene copolymers, propylene-1-hexene copolymers, propylene-1-octene copolymers and propylene-1-decene copolymers. Among them, propylene-ethylene copolymers, propylene-1-butene copolymers and propylene-ethylene-1-butene copolymers are preferable, and propylene-ethylene copolymers are more preferable.

The content of polymer II is preferably from 1 to 50 wt%, more preferably from 5 to 40 wt%, based on the total weight of the heterophasic propylene polymer material.

The content of xylene insoluble fraction (CXIS fraction) in the heterophasic propylene polymer material is preferably from 50 to 99 wt. -%, more preferably from 60 to 95 wt. -%, based on the total weight of the heterophasic propylene polymer material.

The content of xylene soluble fraction (CXS fraction) in the heterophasic propylene polymer material is preferably from 1 to 50 wt. -%, more preferably from 5 to 40 wt. -%, based on the total weight of the heterophasic propylene polymer material.

It is believed that in the present invention, the CXIS component of the heterophasic propylene polymeric material consists essentially of polymer I and the CXS component of the heterophasic propylene polymeric material consists essentially of polymer II.

As heterophasic propylene polymeric materials there may be mentioned, for example: (propylene) - (propylene-ethylene) polymeric materials, (propylene) - (propylene-ethylene-1-butene) polymeric materials, (propylene) - (propylene-ethylene-1-hexene) polymeric materials, (propylene) - (propylene-ethylene-1-octene) polymeric materials, (propylene) - (propylene-1-butene) polymeric materials, (propylene) - (propylene-1-hexene) polymeric materials, (propylene) - (propylene-1-octene) polymeric materials, (propylene) - (propylene-1-decene) polymeric materials, (propylene-ethylene) - (propylene-ethylene-1-butene) polymeric materials, and (propylene-ethylene) - (propylene-ethylene-1-butene) polymeric materials, (propylene-ethylene) - (propylene-ethylene-1-hexene) polymeric material, (propylene-ethylene) - (propylene-ethylene-1-octene) polymeric material, (propylene-ethylene) - (propylene-ethylene-1-decene) polymeric material, (propylene-ethylene) - (propylene-1-butene) polymeric material, (propylene-ethylene) - (propylene-1-hexene) polymeric material, (propylene-ethylene) - (propylene-1-octene) polymeric material, (propylene-ethylene) - (propylene-1-decene) polymeric material, (propylene-1-butene) - (propylene-ethylene) polymeric material, (propylene-1-butene) - (propylene-1-ethylene) polymeric material, (propylene-1-butene) - (propylene-ethylene-1-butene) A polymeric material, (propylene-1-butene) - (propylene-ethylene-1-hexene) polymeric material, (propylene-1-butene) - (propylene-ethylene-1-octene) polymeric material, (propylene-1-butene) - (propylene-ethylene-1-decene) polymeric material, (propylene-1-butene) - (propylene-1-butene) polymeric material, (propylene-1-butene) - (propylene-1-hexene) polymeric material, (propylene-1-butene) - (propylene-1-octene) polymeric material, (propylene-1-butene) - (propylene-1-decene) polymeric material, and (propylene-1-butene) - (propylene-1-decene) polymeric material, A (propylene-1-hexene) - (propylene-1-hexene) polymeric material, a (propylene-1-hexene) - (propylene-1-octene) polymeric material, a (propylene-1-hexene) - (propylene-1-decene) polymeric material, a (propylene-1-octene) - (propylene-1-octene) polymeric material, and a (propylene-1-octene) - (propylene-1-decene) polymeric material.

Here, the description of "(propylene) - (propylene-ethylene) polymeric material" means "a heterophasic propylene polymeric material in which polymer I is a propylene homopolymer and polymer II is a propylene-ethylene copolymer". The same applies to other similar expressions.

As the heterophasic propylene polymer material, a (propylene) - (propylene-ethylene) polymer material, a (propylene) - (propylene-ethylene-1-butene) polymer material, a (propylene-ethylene) - (propylene-ethylene-1-butene) polymer material, or a (propylene-1-butene) - (propylene-1-butene) polymer material is preferred, more preferably a (propylene) - (propylene-ethylene) polymer material.

The intrinsic viscosity ([ eta ] I) of the polymer I is preferably 0.10 to 2.00dL/g, more preferably 0.50 to 1.50dL/g, and still more preferably 0.70 to 1.40 dL/g.

The intrinsic viscosity ([ eta ] II) of the polymer II is preferably 1.00 to 10.00dL/g, more preferably 2.00 to 10.00dL/g, and still more preferably 2.00 to 9.00 dL/g.

The ratio ([ eta ] II/[ eta ] I) of the intrinsic viscosity ([ eta ] II) of the polymer II to the intrinsic viscosity ([ eta ] I) of the polymer I is preferably 1 to 20, more preferably 1 to 10.

Examples of the method for measuring the intrinsic viscosity ([ η ] I) of the polymer I include the following methods: the polymer I formed from the reactor in which the polymer I was formed was withdrawn, and the intrinsic viscosity of the polymer was measured.

The intrinsic viscosity ([ η ] II) of the polymer II can be calculated, for example, using the intrinsic viscosity ([ η ] Total) of the heterophasic propylene polymer material, the intrinsic viscosity ([ η ] I) of the polymer I, and the contents of the polymer II and the polymer I by the following formula (6).

[η]II＝([η]Total-[η]I×XI)/XII (6)

[ η ] Total: intrinsic viscosity (dL/g) of heterophasic propylene polymer materials

[ η ] I: intrinsic viscosity (dL/g) of Polymer I

XI: the ratio of the weight of polymer I relative to the total weight of the heterophasic propylene polymeric material (weight of polymer I/weight of heterophasic propylene polymeric material)

XII: the ratio of the weight of polymer II relative to the total weight of the heterophasic propylene polymeric material (weight of polymer II/weight of heterophasic propylene polymeric material)

Here, XI and XII can be determined from the material balance during the polymerization.

It is noted that XII can be calculated by measuring the heat of fusion of polymer I and the heat of fusion of the heterophasic propylene polymeric material using the following formula.

XII＝1-(ΔHf)T/(ΔHf)P

(Δ Hf) T: heat of fusion (J/g) of heterophasic propylene polymer material

(Δ Hf) P: heat of fusion (J/g) of Polymer I

The intrinsic viscosity ([ eta ] CXIS) of the CXIS component is preferably 0.10 to 2.00dL/g, more preferably 0.50 to 1.50dL/g, and still more preferably 0.70 to 1.40 dL/g.

The intrinsic viscosity ([ eta ] CXS) of the CXS component is preferably 1.00dL/g to 10.00dL/g, more preferably 2.00dL/g to 10.00dL/g, and still more preferably 2.00dL/g to 9.00 dL/g.

The ratio ([ eta ] CXS/[ eta ] CXIS) of the intrinsic viscosity ([ eta ] CXS) of the CXS component to the intrinsic viscosity ([ eta ] CXIS) of the CXIS component is preferably 1 to 20, and more preferably 1 to 10.

The molecular weight distribution (Mw (I)/Mn (I)) of the polymer I is preferably 3.0 or more, more preferably 4.0 or more.

The molecular weight distribution (Mw (CXIS)/Mn (CXIS)) of the CXIS component is preferably 3.0 or more, more preferably 4.0 or more.

The isotactic pentad fraction (also referred to as mmmm fraction) of the component a is preferably 0.950 or more, and more preferably 0.970 or more, from the viewpoint of rigidity and dimensional stability of a molded article formed from the resin composition. The isotactic pentad fraction of the component A may be, for example, 1.000 or less.

An isotactic pentad fraction refers to an isotactic fraction in pentad units. That is, the isotactic pentad fraction indicates the content ratio of a structure in which 5 monomer units derived from propylene are successively meso-bonded when viewed in a pentad unit. When the target component is a copolymer, the target component is a value obtained by measuring a chain of a monomer unit derived from propylene.

In the present specification, the isotactic pentad fraction means utilization¹³Values obtained by C-NMR spectroscopy. Specifically, it will utilize ¹³The ratio of the area of mmmm peak obtained by C-NMR spectrum to the area of the whole absorption peak of the methyl carbon region was taken as the isotactic pentad fraction. In addition, use of¹³A method for measuring the number of isotactic pentads in a C-NMR spectrum is described in Macromolecules,6,925(1973), of A.Zambelli et al. Wherein use is made of¹³The assignment of the absorption peaks obtained by C-NMR spectroscopy is described in Macromolecules,8,687 (1975).

The melt flow rate of the component A at 230 ℃ and under a load of 2.16kgf is preferably 5g/10 min or more, more preferably 10g/10 min to 300g/10 min, from the viewpoint of moldability of the resin composition.

In the present specification, the melt flow rate refers to a value measured in accordance with JIS K7210. In addition, the melt flow rate may be referred to as MFR hereinafter. The measurement temperature of MFR of the component (A), the component (B), the component (E) and the propylene resin composition was 230 ℃ and the measurement temperature of MFR of the component (D) was 190 ℃.

Ethylene-alpha-olefin random copolymer (B)

In the component B, the total content of the monomer units derived from ethylene and the content of the monomer units derived from an α -olefin of C4 or more contained in the component B may be 100% by weight, assuming that the total weight of the component B is 100% by weight.

The alpha-olefin having at least C4 includes, for example, C4 to 12 alpha-olefins. Examples of the C4 to C12 α -olefin include: 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene. Among them, 1-butene, 1-hexene and 1-octene are preferable. The α -olefin may be an α -olefin having a cyclic structure such as vinylcyclopropane or vinylcyclobutane.

Examples of the component B include: ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, ethylene- (3-methyl-1-butene) copolymer, and copolymer of ethylene and α -olefin having a cyclic structure.

In the component B, the content of the monomer unit derived from an α -olefin of C4 or more is preferably 1 to 49% by weight, more preferably 5 to 49% by weight, and further preferably 24 to 49% by weight, based on the total weight of the component B.

The melt flow rate of the component B at 230 ℃ and a load of 2.16kgf is preferably 0.1g/10 min to 80g/10 min.

The density of the component B is preferably 0.85g/cm from the viewpoint of the impact resistance of the molded article³～0.89g/cm³More preferably 0.85g/cm³～0.88g/cm³More preferably 0.85g/cm ³～0.87g/cm³。

Process for producing component B

The component B can be produced by polymerizing ethylene and an alpha-olefin having at least C4 with the use of a polymerization catalyst.

Examples of the polymerization catalyst include homogeneous catalysts typified by metallocene catalysts and ziegler-natta catalysts.

Examples of homogeneous catalysts include: a catalyst comprising a transition metal compound of group 4 of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane; a catalyst comprising a transition metal compound of group 4 of the periodic table having a cyclopentadienyl ring, a compound which forms an ionic complex by reacting with the transition metal compound, and an organoaluminum compound; and a catalyst obtained by modifying inorganic particles (silica, clay mineral, etc.) by supporting thereon a catalyst component (a transition metal compound of group 4 of the periodic table having a cyclopentadienyl ring, a compound forming an ionic complex, an organoaluminum compound, etc.).

Examples of the ziegler-natta type catalyst include: a catalyst obtained by combining a titanium-containing solid transition metal component and an organometallic component.

As the component B, commercially available products can be used. Examples of commercially available component B include: engage (registered trademark) manufactured by dow chemical japan, Tafmer (registered trademark) manufactured by mitsui chemical corporation, NEO-ZEX (registered trademark) manufactured by proyman polymer corporation, ULTZEX (registered trademark), Excellen FX (registered trademark) manufactured by sumitomo chemical corporation, sumikanene (registered trademark), ESPRENE SPO (registered trademark), and the like.

Filling material (C)

The propylene resin composition of the present invention further contains a filler (C).

As the component C, an inorganic filler and an organic filler are exemplified. The propylene resin composition of the present invention may contain only one component C, or may contain two or more components C.

Examples of the inorganic filler include: glass, silicate minerals, alumina, silica, silicon dioxide, titanium oxide, iron oxide, aluminum oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, carbonate minerals, calcium sulfate, magnesium sulfate, basic magnesium sulfate, calcium sulfite, carbon black, and cadmium sulfide.

As the organic filler, there may be mentioned: polyester, aramid, cellulose, and vinylon.

The filler may be in the form of a plate, a needle, or a fiber.

The component C is preferably an inorganic filler, and more preferably talc which is a plate-like silicate mineral, from the viewpoint of rigidity, impact resistance and dimensional stability of the molded article.

The average particle diameter D50[ L ] of component C is preferably 20.0 μm or less, more preferably 15.0 μm or less, from the viewpoint of rigidity, impact resistance and dimensional stability of the molded article. The average particle diameter D50[ L ] of the component C may be 2.0 μm or more, or 4.0 μm or more. The average particle diameter D50[ L ] of the component C is preferably 2.0 to 20.0. mu.m, more preferably 4.0 to 15.0. mu.m. In one embodiment, the average particle diameter D50[ L ] of the component C may be 7.0 to 15.0. mu.m.

The average particle diameter D50[ S ] of component C is preferably 5.0 μm or less, more preferably 3.0 μm or less, from the viewpoint of rigidity, impact resistance and dimensional stability of the molded article.

The average particle diameter D50[ S ] of the component C may be 0.5 μm or more, or 1.0 μm or more. The average particle diameter D50[ S ] of the component C is preferably 0.5 to 5.0. mu.m, more preferably 1.0 to 3.0. mu.m. In one embodiment, the average particle diameter D50[ S ] of the component C may be 2.0 to 5.0. mu.m.

The ratio of the average particle diameter D50[ L ] to the average particle diameter D50[ S ] (D50[ L ]/D50[ S ]) of the component C may be 1.5 or more, or 2.5 or more, from the viewpoint of rigidity and dimensional stability of the molded article. D50[ L ]/D50[ S ] may be 10 or less or 8 or less. D50[ L ]/D50[ S ] can be 1.5-10, also can be 1.5-8, also can be 2.5-10, also can be 2.5-8. In one embodiment, D50[ L ]/D50[ S ] may be 3.0 to 8.

The "average particle diameter D50[ L ]" refers to a particle diameter (50% equivalent particle diameter) determined based on volume-based particle diameter distribution measurement data measured by a laser diffraction method according to a method defined in JIS R1629, in which the cumulative particle number from the smaller particle diameter side in the particle diameter distribution measurement data is 50%. The particle size thus defined is generally referred to as "50% equivalent particle size" and is denoted by "D50".

In the present specification, the "average particle diameter D50[ S ]" refers to a particle diameter (50% equivalent particle diameter) determined based on volume-based particle diameter distribution measurement data measured by a centrifugal sedimentation method according to a method defined in JIS R1619, in which the cumulative particle number from the smaller particle diameter side in the particle diameter distribution measurement data is 50%.

The larger the ratio of the average particle diameter D50[ L ] to the average particle diameter D50[ S ] (D50[ L ]/D50[ S ]), the more excellent the rigidity and dimensional stability of the molded article.

Ethylene-alpha-olefin block copolymer (D)

The component D of the present invention is a xylene-soluble component of 70% by weight or less (wherein the total amount of the component D is 100% by weight) and has a density of 0.865g/cm³～0.867g/cm³The ethylene- α -olefin block copolymer of (1). Since the xylene-soluble component of the ethylene- α -olefin random copolymer is usually 90% by weight or more, the "ethylene- α -olefin block copolymer having a xylene-soluble component of 70% by weight or less" can be regarded as "ethylene- α -olefin block copolymer".

Ethylene- α -olefin block copolymers are block copolymers in which a semi-crystalline segment (also referred to as a "hard segment") and an amorphous segment (also referred to as a "soft segment") are covalently bonded. Semi-crystalline and amorphous segments can be formed by varying the ratio of alpha-olefin to ethylene in the segment, respectively. Component D is produced by using a catalyst system in a single polymerization reactor that utilizes a chain shuttling agent that moves the growing chain between two different catalysts having different monomer selectivities. Ingredient D is available from dow chemical company, midfuse, midland, michigan under the trademark INFUSE.

In component D, two or more chemically different regions or segments (also referred to as "blocks") are bonded in a linear, pendant, or graft manner. The ethylene-alpha-olefin block copolymer may also be a multi-block copolymer.

The term "multi-block copolymer" refers to a polymer comprising two or more chemically distinct regions or segments (also referred to as "blocks") that are linearly bonded, i.e., a polymer comprising chemically distinct units that are bonded to a polymerized ethylenic functionality in an end-to-end manner, rather than in pendent or grafted fashion. The amount or type of comonomer incorporated therein, density, crystallinity, size of crystallites believed to be formed by the polymers of such compositions, type (isotactic or syndiotactic) or degree of tacticity, local ordering or local disordering, amount of branches comprising long or hyper-branches, homogeneity or other chemical or physical properties are different for the blocks. The multi-block copolymer can be an ethylene/alpha-olefin multi-block copolymer and (a) is a fraction that elutes between about 40 ℃ to about 130 ℃ when fractionated using Temperature Rising Elution Fractionation (TREF), characterized by having a block index of at least 0.5 and up to 1 and a molecular weight distribution (PDI, Mw/Mn, MWD) greater than 1.3; or (b) is characterized by having an average block index of greater than 0 and 1.0 or less and a MWD of greater than 1.3. In addition, ethylene multi-block interpolymers typically have at least one of the following properties: (i) a molecular weight distribution of greater than 1.3, (ii) a density of less than 0.90g/cc, (iii) a 2% secant modulus of less than 150 megapascals (mPa) as determined by ASTM D-882-02, (iv) a melting point of less than 125 ℃, (v) an olefin content of at least 10 wt% and less than 80 wt%, based on the weight of the interpolymer, (vi) a Tg of less than-35 ℃, and (vii) a Melt Index (MI) of less than 100 grams per 10 minutes (g/10 minutes). Multiblock copolymers are disclosed in U.S. patent application No. 11/376835, filed on 3/15/2006, the entire contents of which are incorporated herein by reference. Propylene/α -olefin multi-block copolymers are disclosed in U.S. patent application No. 11/686444, filed on 3-15-2007, the entire contents of which are incorporated herein by reference.

In another embodiment, the block copolymer generally does not have a third class of blocks that contain different comonomers (which can be multiple). In yet another embodiment, the hard and soft segments each have a substantially random distribution of monomers or comonomers within the block. That is, neither the hard segment nor the soft segment contains two or more sub-segments (or sub-blocks) having different compositions, such as a terminal segment, and having a composition substantially different from the rest of the block.

Multiblock polymers typically contain varying amounts of hard and soft segments. Hard segments refer to blocks of polymerized units in which ethylene is present in an amount greater than about 95 weight percent, preferably greater than about 98 weight percent, based on the weight of the polymer. That is, the comonomer content (content of monomers other than ethylene) in the hard segments is less than about 5 wt%, preferably less than about 2 wt%, based on the weight of the polymer. In some embodiments, the hard segments are composed entirely or substantially entirely of ethylene. Soft segments, on the other hand, refer to blocks of polymerized units having a comonomer content (content of monomers other than ethylene) of greater than about 5 weight percent, preferably greater than about 8 weight percent, greater than about 10 weight percent, or greater than about 15 weight percent, based on the weight of the polymer. In some embodiments, the comonomer content in the soft segment can be greater than about 20 wt.%, greater than about 25 wt.%, greater than about 30 wt.%, greater than about 35 wt.%, greater than about 40 wt.%, greater than about 45 wt.%, greater than about 50 wt.%, or greater than about 60 wt.%. In one embodiment, component D comprises soft segments of an ethylene- α -olefin random copolymer.

In many cases the soft segments can be present in the block copolymer in an amount of from about 1 to about 99 weight percent, relative to the total weight of the block copolymer, preferably from about 5 to about 95 weight percent, from about 10 to about 90 weight percent, from about 15 to about 85 weight percent, from about 20 to about 80 weight percent, from about 25 to about 75 weight percent, from about 30 to about 70 weight percent, from about 35 to about 65 weight percent, from about 40 to about 60 weight percent, or from about 45 to about 55 weight percent, relative to the total weight of the block copolymer. The hard segments may also be present in the same range. The soft segment weight% and the hard segment weight% can be calculated based on data obtained by DSC or NMR. Such methods and calculations are disclosed in U.S. patent application No. 11/376835 filed on 3.15.2006 under the name of Colin l.p. shann, Lonnie hazlit et al, and assigned to the dow glob technology company, filed concurrently under the name of "ethylene/a-olefin block interpolymer," the entire disclosure of which is incorporated herein by reference.

Where the term "crystalline" is used, it refers to a polymer having a first order transition or crystalline melting point (Tm) as determined by Differential Scanning Calorimetry (DSC) or equivalent technique.

The term may be used interchangeably with the term "semicrystalline". The term "amorphous" refers to a polymer that does not have a crystalline melting point as determined by Differential Scanning Calorimetry (DSC) or equivalent technique.

In one embodiment, component D has a density of 0.865g/cm³～0.867g/cm³Preferably 0.866g/cm³～0.867g/cm³。

In one embodiment, the component D has a melt flow rate of 0.5g/10 min to 10g/10 min, preferably 1g/10 min to 8g/10 min at 190 ℃ under a load of 2.16 kgf.

The MFR of the component D is preferably 0.5g/10 min or more from the viewpoint of moldability (flowability) of the resin composition, and the MFR of the component D is preferably 10g/10 min or less from the viewpoint of dimensional stability of the obtained molded article and hinge resistance (ヒンジ resistance) of a weld portion.

The weld refers to a linear trace that is generated between resins because molten resins do not adhere to each other when the molten resin composition flows into the mold cavity from two gates and the molten resins merge with each other, or when the molten resins branched in the mold cavity merge with each other. If the adhesion between the molten resins is poor, the hinge resistance of the weld portion is poor, and the weld portion is likely to break.

Propylene-based Polymer (E) having characteristic I

Component E is a propylene-derived monomer unit having 50% by weight or more and a shear rate of 61 seconds^-1The extrusion swell ratio and the shear rate were 6080 seconds^-1The absolute value of the difference in the die swell ratio is 0.35 or less (characteristic I). The propylene resin of the present invention is excellent in dimensional stability and hinge resistance at weld jointsThe composition preferably contains component E.

In general, when the propylene-based polymer has a long-chain branch, the propylene-based polymer has the property I.

The long chain branch is a branched structure formed of a molecular chain having a main chain with a carbon number of several tens or more. Unlike a short chain branch having several carbon atoms, which is formed by copolymerization with an α -olefin such as 1-butene.

As the component E, there may be mentioned: at least one long-chain branched propylene-based polymer selected from the group consisting of a long-chain branched propylene polymer (E1), a long-chain branched propylene-ethylene block copolymer (E2) comprising a propylene polymer portion and an ethylene-propylene random copolymer portion, and a long-chain branched propylene-ethylene random copolymer (E3).

Characteristic I

Shear rate of component E was 61 seconds^-1The extrusion swell ratio and the shear rate were 6080 seconds^-1The absolute value of the difference in the die swell ratio is 0.35 or less, preferably 0.2 or less, and more preferably 0.1 or less.

The die swell ratio at each shear rate was determined by the following method. A capillary rheometer (e.g., Capilograph ID manufactured by Toyo Seiki Seisaku-Sho K.K.) having a capillary with a diameter (D) of 1mm and a length (L) of 40mm, i.e., L/D of 40 was used, and the capillary rheometer was subjected to a test at a temperature of 220 ℃ and a shear rate of 61 seconds^-1(the plunger was pressed at a rate of 5 mm/min) and the molten sample was extruded from the outlet of the capillary to prepare a strand. The diameter of the strand at a position 12mm below the outlet of the capillary in the vertical direction was measured by a laser. The die swell ratio is represented by the following formula.

The ratio of die swell to die swell (mm) of strand/diameter of capillary (mm)

Similarly, the shear rate was 6080 seconds at a test temperature of 200 ℃ and a test temperature of^-1(plunger pressure rate of 500 mm/min) under the conditions of the molten sample extrusion, found the shear rate of 6080 seconds^-1Extrusion swell ratio at the time of extrusion.

The extrusion swell ratio at each shear rate was determined, and then the shear rate was calculated as61 seconds^-1The extrusion swell ratio and the shear rate were 6080 seconds^-1Absolute value of the difference in the die swell ratio. The absolute value Δ of the difference in the die swell ratio is represented by the following formula.

Δ | (shear rate 6080 sec) ^-1Extrusion die swell ratio of (shear rate of 61 seconds) (^-1Extrusion swell ratio) of cells

Shear rate of component E was 61 seconds^-1The die swell ratio is preferably 1.7 or more, more preferably 1.9 or more.

The component E preferably has at least one of the following characteristics II to III.

Characteristic II: the Melt Flow Rate (MFR) (230 ℃ C., load 2.16kg) is 0.1g/10 min to 10g/10 min.

Property III: the crystallization time at 135 ℃ is 150 seconds or less.

Characteristic II

The MFR (230 ℃ C., load 2.16kg) of component E is 0.1g/10 min to 10g/10 min, preferably 0.1g/10 min to 9g/10 min, and more preferably 1g/10 min to 9g/10 min.

The MFR of the component E is preferably 0.1g/10 min or more from the viewpoint of the flowability (moldability) of the resin composition. On the other hand, the MFR of the component E is preferably 10g/10 min or less from the viewpoint of the anti-stringing property and the balance of physical properties (impact strength).

The MFR value of component E was measured by the method described in JIS K7210 (measurement temperature: 230 ℃ C., load: 2.16 kg).

Characteristic III

The crystallization time of the component E at 135 ℃ is 150 seconds or less, preferably 145 seconds or less, more preferably 140 seconds or less.

When the number of long-chain branches of the propylene-based polymer is increased, the crystallization time can be shortened.

Crystallization speed (crystallization time, T1/2, unit: second)

The measurement was performed using a differential scanning calorimeter (DSC model VII manufactured by Perkin Elmer). As for the measurement conditions, 10mg of the sample was placed in a nitrogen atmosphere in advance, isothermal crystallization was carried out at a crystallization temperature of 135 ℃ for 10 minutes, and the half width of the peak of the obtained endothermic curve was measured as the crystallization time. The shorter the crystallization time, the faster the crystallization speed.

Process for producing component E

Branching can generally be achieved using specific catalysts, i.e. specific single-site catalysts, or by chemical modification. For the preparation of branched polypropylene using a specific catalyst, reference is made to european patent No. 1892264. For branched polypropylene obtained by chemical modification see european patent application publication No. 0879830a 1. In such cases, the branched polypropylene is also referred to as high melt strength polypropylene. The high melt strength polypropylene (HMS-PP) of the present invention is obtained by chemical modification of polypropylene (PP) as described in more detail below. HMS-PP is sold under the trade name Daploy (trademark) by Borealis AG and under the trade name WAYMAX (trademark) by Japan Polypropylene corporation, respectively.

The content of each component

In the propylene resin composition of the present invention, the content of the component a is 30 to 65 parts by weight, may be 40 to 65 parts by weight, or may be 40 to 60 parts by weight, based on 100 parts by weight of the total of the contents of the components a to D, from the viewpoint of dimensional stability (linear expansion coefficient) of a molded article.

In the propylene resin composition of the present invention, the content of the component B is 10 to 40 parts by weight, may be 10 to 30 parts by weight, or may be 10 to 25 parts by weight, based on 100 parts by weight of the total content of the components a to D, from the viewpoint of dimensional stability (linear expansion coefficient) of a molded article.

In the propylene resin composition of the present invention, the content of the component C is 10 to 40 parts by weight, may be 10 to 35 parts by weight, or may be 15 to 25 parts by weight, based on 100 parts by weight of the total of the contents of the components a to D, from the viewpoint of dimensional stability (linear expansion coefficient) of a molded article. In one embodiment, the content of the component C may be 25 to 35 parts by weight, or 30 to 35 parts by weight, based on 100 parts by weight of the total content of the components a to D, from the viewpoint of the elastic modulus.

In the propylene resin composition of the present invention, the content of the component D is 0.1 to 10 parts by weight, may be 1 to 10 parts by weight, or may be 2 to 8 parts by weight, based on 100 parts by weight of the total of the contents of the components a to D, from the viewpoints of dimensional stability (linear expansion coefficient) and hinge resistance of a molded article.

When the propylene resin composition of the present invention contains the component E, the content of the component E is preferably 5 parts by weight or less, may be 0.1 to 5 parts by weight, may be 0.5 to 4 parts by weight, or may be 1 to 3 parts by weight, based on 100 parts by weight of the total content of the components a to D, from the viewpoint of a balance among the hinge resistance, moldability (flowability), and dimensional stability (linear expansion coefficient).

The total content of the components a to D or the total content of the components a to E is preferably 50% by weight or more based on the total weight of the propylene resin composition of the present invention.

Method for producing propylene resin composition

The propylene resin composition of the present invention can be obtained by melt-kneading the respective raw material components. The temperature during the melting and mixing can be more than 180 ℃, also can be 180-300 ℃, and also can be 180-250 ℃.

In the melt-kneading, a Banbury mixer, a single-screw extruder, a twin-screw co-rotating extruder, or the like can be used.

The order of mixing the raw material components is not particularly limited. For example, the components a to D (or the components a to E) may be kneaded at once, or a part of the components a to D (or the components a to E) may be kneaded, and then the obtained kneaded product may be kneaded with other components.

The shape of the propylene resin composition is not particularly limited, and the propylene resin composition may be in the form of, for example, a thread, a sheet, a plate or a pellet. The granular resin composition can be produced, for example, by forming a linear resin composition and then cutting the linear resin composition into a suitable length.

From the viewpoint of moldability of the resin composition and production stability in the case of producing a molded article, the shape of the resin composition before molding into a molded article is preferably a granular shape having a length of about 1mm to about 50 mm.

The propylene resin composition of the present invention may contain components other than those described above. Examples of such components include: neutralizing agents, antioxidants, ultraviolet absorbers, nucleating agents, lubricants, antistatic agents, antiblocking agents, processing aids, organic peroxides, colorants (inorganic pigments, organic pigments, pigment dispersants), foaming agents, foam nucleating agents, plasticizers, flame retardants, crosslinking agents, crosslinking aids, brighteners, antibacterial agents, and light diffusers. Examples of the nucleating agent include: carboxylic acid metal salts such as lithium benzoate, sodium benzoate, aluminum benzoate, 4-tert-butylbenzoate aluminum salt, and sodium adipate; sodium bis (4-tert-butylphenyl) phosphate, acidic phosphate metal salt; and polyol derivatives such as dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, and bis (dimethylbenzylidene) sorbitol. Among these nucleating agents, metal salts of carboxylic acids and bis (dimethylbenzylidene) sorbitol are preferable from the viewpoint of dimensional stability. The propylene resin composition of the present invention may contain only one of these components, or may contain two or more of these components.

When the propylene resin composition of the present invention contains a nucleating agent, the content of the nucleating agent may be 0.01 to 1.0 part by weight, or 0.05 to 0.5 part by weight, or 0.1 to 0.5 part by weight, based on 100 parts by weight of the total of the contents of the components a to D, from the viewpoint of dimensional stability.

Properties of propylene resin composition

In one embodiment, the propylene resin composition of the present invention has a melt flow rate (temperature 230 ℃ C., load 2.16kgf) of preferably 15g/10 min to 70g/10 min, or 25g/10 min to 65g/10 min, or 35g/10 min to 60g/10 min. From the viewpoint of moldability, the MFR of the propylene resin composition is preferably 15g/10 min or more. The MFR of the propylene resin composition is preferably 70g/10 min or less from the viewpoint of the impact strength of the resulting molded article.

In one embodiment, the propylene resin composition of the present invention has a melt flow rate (temperature 230 ℃ C., load 2.16kgf) of preferably 15g/10 min to 50g/10 min, or 15g/10 min to 35g/10 min, or 15g/10 min to 30g/10 min, from the viewpoint of dimensional stability.

In one embodiment, the density of the propylene resin composition of the present invention is preferably 1.1g/cm³Hereinafter, more preferably 1.08g/cm³Hereinafter, more preferably 1.06g/cm³The following.

In one embodiment, the density of the propylene resin composition of the present invention is preferably 1.08g/cm from the viewpoint of dimensional stability³～1.2g/cm³More preferably 1.1g/cm³～1.18g/cm³。

The density of the propylene resin composition of the present invention was measured by the underwater substitution method, which is method a described in JIS K7112.

The flexural modulus of the propylene resin composition of the present invention is measured according to the method defined in JIS K7171. A test piece having a thickness of 4.0mm, which was molded by a method of producing an injection molded article described later, was used, and the measurement was performed under conditions of a span length of 64mm, a load rate of 2.0 mm/min, and a measurement temperature of 23 ℃.

The propylene resin composition of the present invention can be used as a material for forming a molded article by molding. The propylene resin composition of the present invention is preferably used as a material for injection molding. An example of an injection molded article produced by using the propylene resin composition of the present invention as an injection molding material will be described below.

Shaped body

The molded article of the present invention comprises the propylene resin composition of the present invention. The molded article of the present invention is excellent in dimensional stability. The molded body is preferably an injection molded body. In one embodiment, the injection molded article of the present invention is less likely to break at the weld portion and has excellent hinge resistance.

The injection molded article can be produced by injection molding. Examples of the injection molding method include: general injection compression molding, injection foam molding, supercritical injection foam molding, ultrahigh-speed injection molding, injection compression molding, gas-assist injection molding, sandwich foam molding, and insert-on-substrate injection molding. The shape of the injection-molded body is not particularly limited.

The injection molded article of the present invention can be preferably used for, for example, automobile material applications, household electrical appliance material applications and container applications, and among these, automobile interior and exterior parts applications are preferable. Examples of the automotive interior and exterior parts include: door trim, pillar, instrument panel, and bumper.

Examples

The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

In examples and comparative examples, the following raw materials were used.

[ component A: propylene Polymer

The following propylene-based polymers (BCPP1, BCPP2, BCPP3, BCPP4, homo pp1, and homo pp2) were prepared as the component a.

BCPP 1: (propylene) - (propylene-ethylene) polymeric materials

"C7100-50 NA" manufactured by Blassco "

MFR (measured at a temperature of 230 ℃ under a load of 2.16 kgf): intrinsic viscosity 52g/10 min: ([ η ] CXIS): 0.95dL/g, ([ η ] CXS): 1.61dL/g

Isotactic pentad fraction: 0.9615

CXIS component amount: 74.3% by weight

Mw/Mn of CXIS component: 4.4

CXS component amount: 25.7% by weight

Ethylene content in propylene-ethylene random copolymer: 48.9% by weight

Shear rate 6080 sec^-1Extrusion swell ratio of time: 1.35

Shear rate of 61 seconds^-1Extrusion swell ratio of time: 0.94

Difference in extrusion swell ratio: 0.41

BCPP 2: (propylene) - (propylene-ethylene) polymeric materials

Is produced by a gas phase polymerization method in the presence of a polymerization catalyst obtained by the method described in example 1 of Japanese patent application laid-open No. 2004-182981.

MFR (measured at a temperature of 230 ℃ under a load of 2.16 kgf): intrinsic viscosity at 129g/10 min: ([ η ] CXIS): 1.02dL/g, ([ η ] CXS): 3.96dL/g

Isotactic pentad fraction: 0.9842

CXIS component amount: 93.6% by weight

Mw/Mn of CXIS component: 6.3

CXS component amount: 6.4% by weight

Ethylene content in propylene-ethylene random copolymer: 39.0% by weight

Shear rate 6080 sec^-1Extrusion swell ratio of time: 1.80

Shear rate of 61 seconds^-1Extrusion swell ratio of time: 0.94

Difference in extrusion swell ratio: 0.86

BCPP 3: (propylene) - (propylene-ethylene) polymeric materials

Is produced by a gas phase polymerization method in the presence of a polymerization catalyst obtained by the method described in example 1 of Japanese patent application laid-open No. 2004-182981.

MFR (measured at a temperature of 230 ℃ under a load of 2.16 kgf): intrinsic viscosity 43g/10 min: ([ η ] CXIS): 1.15dL/g, ([ η ] CXS): 1.80dL/g

Isotactic pentad fraction: 0.9843

CXIS component amount: 81.1% by weight

Mw/Mn of CXIS component: 6.8

CXS component amount: 18.9% by weight

Ethylene content in propylene-ethylene random copolymer: 49.5% by weight

Shear rate 6080 sec^-1Extrusion swell ratio of time: 1.98

Shear rate of 61 seconds^-1Extrusion swell ratio of time: 1.25

Difference in extrusion swell ratio: 0.73

BCPP 4: (propylene) - (propylene-ethylene) polymeric materials

Is produced by a gas phase polymerization method in the presence of a polymerization catalyst obtained by the method described in example 1 of Japanese patent application laid-open No. 2004-182981.

MFR (measured at a temperature of 230 ℃ under a load of 2.16 kgf): intrinsic viscosity 18g/10 min: ([ η ] CXIS): 1.15dL/g, ([ η ] CXS): 7.60dL/g

Isotactic pentad fraction: 0.9832

CXIS component amount: 75.7% by weight

Mw/Mn of CXIS component: 6.8

CXS component amount: 24.3% by weight

Ethylene content in propylene-ethylene random copolymer: 41.1% by weight

Shear rate 6080 sec^-1Extrusion swell ratio of time: 2.17

Shear rate of 61 seconds^-1Extrusion swell ratio of time: 1.48

Difference in extrusion swell ratio: 0.69

HOMOPP 1: propylene homopolymer

Is produced by a gas phase polymerization method in the presence of a polymerization catalyst obtained by the method described in example 1 of Japanese patent application laid-open No. 2004-182981.

MFR (measured at a temperature of 230 ℃ under a load of 2.16 kgf): intrinsic viscosity 107g/10 min: ([ η ]): 0.92dL/g

Isotactic pentad fraction: 0.9811

Mw/Mn：5.4

Shear rate 6080 sec^-1Extrusion swell ratio of time: 1.54

Shear rate of 61 seconds^-1Extrusion swell ratio of time: 0.83

Difference in extrusion swell ratio: 0.71

HOMOPP 2: propylene homopolymer

Is produced by a gas phase polymerization method in the presence of a polymerization catalyst obtained by the method described in example 1 of Japanese patent application laid-open No. 2004-182981.

MFR (measured at a temperature of 230 ℃ under a load of 2.16 kgf): intrinsic viscosity at 139g/10 min: ([ η ]): 1.04dL/g

Isotactic pentad fraction: 0.9843

Mw/Mn：7.0

Shear rate 6080 sec^-1Extrusion swell ratio of time: 2.22

Shear rate of 61 seconds^-1Extrusion swell ratio of time: 1.12

Difference in extrusion swell ratio: 1.10

In BCPP 1-4, "ethylene content in propylene-ethylene random copolymer" means the ethylene content (the content of monomer units derived from ethylene based on the total weight of polymer II) in polymer II.

MFR, intrinsic viscosity and isotactic pentad fraction were measured in the above-mentioned manner, and the contents of CXIS component and CXS component, the ethylene content in polymer II and the molecular weight distribution were calculated by the following methods.

Content of CXIS component and CXS component

2g of a heterophasic propylene polymer material (hereinafter, "the weight of the heterophasic propylene polymer material" is referred to as "a") was weighed and dissolved in boiling xylene under heating for 2 hours. Then, it was cooled to 20 ℃ and then filtered using filter paper. The filtrate after filtration was concentrated under reduced pressure by a rotary evaporator to obtain a CXS component. The CXS component thus obtained was weighed (hereinafter, "weight of CXS component" is referred to as "b"). The amounts of the CXIS component and the CXS component in the heterophasic propylene polymer material are calculated by the following formula using the values a and b. The solid remaining on the filter paper was dried under vacuum to obtain a CXIS component. The CXIS fraction obtained was used for evaluation of molecular weight distribution.

CXS component amount (% by weight) — (b/a) × 100

The amount of the CXIS component (% by weight) is 100-CXS component (% by weight)

Ethylene content in Polymer II

The ethylene content in Polymer II is determined under the conditions¹³The C-NMR spectrum was obtained based on the report of Kakugo et al (Macromolecules,15,1150-1152 (1982)). About¹³C-NMR spectrum was measured under the following conditions using a sample obtained by uniformly dissolving about 200mg of the heterophasic propylene polymer material in 3mL of o-dichlorobenzene in a test tube having a diameter of 10 mm.

Measuring temperature: 135 deg.C

Pulse repetition time: 10 seconds

Pulse width: 45 degree

The accumulation times are as follows: 2500 times (times)

Molecular weight distribution

The molecular weight distribution of the propylene homopolymer was determined by measuring the weight average molecular weight (Mw (a)) and the number average molecular weight (Mn (a)) of the propylene homopolymer by GPC and calculating the ratio of Mw to Mn (Mw/Mn). The molecular weight distribution of the CXIS component is determined by measuring the weight average molecular weight (Mw (a)) and the number average molecular weight (Mn (a)) of the CXIS component obtained by the above-described procedure by GPC and calculating the ratio of Mw to Mn (Mw/Mn). The measurement conditions of GPC are as described above.

Component B: ethylene-alpha-olefin random copolymer

The following ethylene- α -olefin random copolymers (EBR and EOR1) were prepared as component B. The MFR and the contents of the CXIS component and the CXS component were measured by the above-described methods.

EBR: ethylene-1-butene random copolymer

"ENR 7467" manufactured by the Dow chemical company "

Density: 0.862g/cm³

MFR (measured at a temperature of 230 ℃ under a load of 2.16 kgf): 2.5g/10 min

CXIS component amount: 0.0% by weight

CXS component amount: 100.0% by weight

EOR 1: ethylene-1-octene random copolymer

"EG 8842" manufactured by the Dow chemical company "

Density: 0.857g/cm³

MFR (measured at a temperature of 230 ℃ under a load of 2.16 kgf): 2.7g/10 min

CXIS component amount: 1.4% by weight

CXS component amount: 98.6% by weight

Component C: filling material

The following fillers (TALCs 1 and 2) were prepared as component C.

TALC 1: talc

"Jetfine 3 CA" manufactured by Imerys "

Average particle diameter D50[ L ] (laser diffraction method, 50% equivalent particle diameter): 4.39 μm

Average particle diameter D50[ S ] (centrifugal sedimentation method, 50% equivalent particle diameter): 1.73 μm

TALC 2: talc

"HAR T84" manufactured by Imerys "

Average particle diameter D50[ L ] (laser diffraction method, 50% equivalent particle diameter): 12.60 μm

Average particle diameter D50[ S ] (centrifugal sedimentation method, 50% equivalent particle diameter): 3.47 μm

Herein, the average particle diameter D50[ L ] of talc was measured by dispersing particles under the following conditions by a method prescribed in JIS R1629 using a MICROTRAC particle size analyzer MT-3300EXII manufactured by Nikkiso K.K.

Dispersion treatment of particles

Dispersion medium: ethanol

The device comprises the following steps: homogenizer

Output power: 40W

Treatment time: 10 minutes

Further, D50[ S ] was measured by dispersing particles under the following conditions by a method prescribed in JIS R1619 using a centrifugal sedimentation type particle size distribution measuring apparatus SA-CP3 manufactured by Shimadzu corporation.

Dispersion treatment of particles

Dispersion medium: ethanol

The device comprises the following steps: w-113MkII manufactured by this Multi-Electron Ltd

Output power: 110W 24kHz

Treatment time: 10 minutes

Component D: ethylene-alpha-olefin block copolymer

The following ethylene- α -olefin block copolymer (OBC1) was prepared as component D. The MFR and the contents of the CXIS component and the CXS component were measured by the above-described methods.

OBC 1: ethylene 1-octene block copolymer

"INFUSE D9507" manufactured by the Dow chemical company "

Density: 0.866g/cm³

MFR (measured at a temperature of 190 ℃ under a load of 2.16 kgf): 5g/10 min

CXIS component amount: 40.3% by weight

CXS component amount: 59.7% by weight

OBC 2: ethylene 1-octene block copolymer

"INFUSE D9100" manufactured by Dow chemical company "

Density: 0.877g/cm³

MFR (measured at a temperature of 190 ℃ under a load of 2.16 kgf): 1g/10 min

CXIS component amount: 82.8% by weight

CXS component amount: 17.2% by weight

Component E: propylene-based polymer having characteristic I

The following propylene-based polymer (HMS1) was prepared as component E. Incidentally, MFR and molecular weight distribution were measured in accordance with the above-mentioned methods. The absolute values of the difference between the crystallization time and the ratio of the die swell were measured by the following methods.

HMS 1: propylene homopolymer

"WB 140 HMS" manufactured by Borealis "

MFR (measured at a temperature of 230 ℃ under a load of 2.16 kgf): 1.8g/10 min

Mw/Mn：4.7

Shear rate 6080 sec^-1Extrusion swell ratio of time: 2.22

Shear rate of 61 seconds^-1Extrusion swell ratio of time: 2.18

Absolute value of difference in die swell ratio: 0.04

Crystallization time: 132 seconds

HMS 2: propylene homopolymer

"MFX 8" manufactured by Japan Polypropylene corporation "

MFR (measured at a temperature of 230 ℃ under a load of 2.16 kgf): 1.0g/10 min

Mw/Mn：4.1

Shear rate 6080 sec^-1Extrusion swell ratio of time: 2.15

Shear rate of 61 seconds^-1Extrusion swell ratio of time: 2.24

Absolute value of difference in die swell ratio: 0.09

Crystallization time: 639 seconds

HMS 3: propylene homopolymer

"MFX 3" manufactured by Japan Polypropylene corporation "

MFR (measured at a temperature of 230 ℃ under a load of 2.16 kgf): 8.9g/10 min

Mw/Mn：3.4

Shear rate 6080 sec^-1Extrusion swell ratio of time: 2.10

Shear rate of 61 seconds^-1Extrusion swell ratio of time: 1.93

Absolute value of difference in die swell ratio: 0.17

Crystallization time: 848 seconds

HMS 4: (propylene) - (propylene-ethylene) polymeric materials

"EX 8000" manufactured by Japan Polypropylene corporation "

MFR (measured at a temperature of 230 ℃ under a load of 2.16 kgf): 1.3g/10 min

Mw/Mn：6.8

CXIS component amount: 94.5% by weight

CXS component amount: 5.5% by weight

Shear rate 6080 sec^-1Extrusion swell ratio of time: 2.15

Shear rate of 61 seconds^-1Extrusion swell ratio of time: 1.97

Absolute value of difference in die swell ratio: 0.18

Crystallization time: 481 second

Crystallization time (T1/2, unit: second)

The measurement was performed using a differential scanning calorimeter (DSC model VII manufactured by Perkin Elmer). As for the measurement conditions, 10mg of the sample was placed in a nitrogen atmosphere in advance, isothermal crystallization was carried out at a crystallization temperature of 135 ℃ for 10 minutes, and the half width of the peak of the obtained endothermic curve was measured as the crystallization time.

Method for measuring absolute value Delta of difference in die swell ratio (Unit:.)

A capillary rheometer (Capilograph ID manufactured by Toyo Seiki Seisaku-Sho K.K.) having a capillary with a diameter (D) of 1mm and a length (L) of 40mm, i.e., L/D of 40 was used, and the capillary rheometer was subjected to a test at a temperature of 220 ℃ and a shear rate of 61 seconds ^-1(the plunger was pressed at a rate of 5 mm/min) and the shear rate was 6080 seconds^-1(the plunger was pressed at a rate of 500 mm/min), the molten composition was extruded from the outlet of the capillary, and a strand was produced. The diameter of the strand at a position 12mm below the outlet of the capillary in the vertical direction was measured by a laser. The die swell ratio at each shear rate is represented by the following formula.

The ratio of die swell to die swell (mm) of strand/diameter of capillary (mm)

The die swell ratio at each shear rate was determined, and the shear rate was calculated to be 61 seconds^-1The extrusion swell ratio and the shear rate were 6080 seconds^-1Absolute value of the difference in the die swell ratio.

That is, the absolute value Δ of the difference in the die swell ratio is represented by the following formula.

Δ | (shear rate 6080 sec)^-1Extrusion die swell ratio of (shear rate of 61 seconds) (^-1Extrusion swell ratio) of cells

Examples 9 and 10 of the present invention contained 0.2 parts by weight of calcium 1, 2-cyclohexanedicarboxylate (content: 66% by weight) as a nucleating agent (Hyperform HPN-20E manufactured by Milliken Japan K.K.) per 100 parts by weight of the propylene resin composition as other components.

Examples 1 to 10 and comparative examples 1 to 4

Production of propylene resin composition

Propylene-based polymers (BCPP1, BCPP2, BCPP3, BCPP4, homo pp1, homo pp2), ethylene- α -olefin random copolymers (EBR, EOR1), fillers (TALC1, TALC2), ethylene- α -olefin block copolymers (OBC1, OBC2), and propylene-based polymers having characteristic I (HMS1, HMS2, HMS3, HMS4) were prepared in amounts shown in table 1.

The prepared components were uniformly premixed by a Henschel mixer or a tumbler, and then kneaded and extruded by a twin-screw kneading extruder (TEX 44. alpha. II-49BW-3V manufactured by Nippon Steel works, Ltd.) under conditions of an extrusion amount of 70 kg/hr, 200 ℃, a screw rotation speed of 300rpm, and a vent suction, to produce a resin composition. The physical properties of the obtained resin composition are shown in table 1 below.

Production of injection molded article for evaluation of Density and flexural modulus of elasticity

The obtained resin composition was injection-molded under the following conditions in the range described in JIS K7152 to produce an injection-molded article for density evaluation. The resin composition melted in the injection molding machine is supplied into the mold cavity from the gate by the injection molding machine.

An injection molding machine: m70 (mold clamping force 70 ton, cylinder diameter 32mm) manufactured by Kabushiki Kaisha machine, die cavity shape: ISO mold type A

Barrel temperature: 197 deg.C

Temperature of the die: 38 deg.C

Injection speed: 20 mm/sec

Cooling time: 8 seconds

Production of injection-molded article for evaluation of coefficient of linear expansion

The obtained resin composition was injection-molded under the following conditions to prepare an injection-molded article for evaluation shown in fig. 1. The resin composition melted in the injection molding machine is supplied into the mold cavity from the gate by the injection molding machine.

An injection molding machine: SE180D (mold clamping force 180 ton, cylinder diameter 50mm) manufactured by Sumitomo heavy machinery industry Co., Ltd

The shape of the die cavity is as follows: 100mm (width) × 400mm (length) × 3mm (thickness)

Pouring: 1 sector gate in the center of 100mm side

Barrel temperature: 220 deg.C

Temperature of the die: 50 deg.C

Injection speed: 23 mm/sec

Cooling time: 30 seconds

FIG. 1 is a schematic view of an injection-molded article for evaluation. An injection molded body 10 shown in fig. 1 has a first resin portion 1 corresponding to a mold shape and a second resin portion 2 corresponding to a gate shape. First resin part 1 is a plate-shaped resin part having a width L1 of 100mm, a length L2 of 400mm, and a thickness (not shown) of 3 mm. In addition, in the injection-molded bodies formed in the present embodiment and the comparative example, the lengths L3, L4, and L5 and the thicknesses (not shown) of the sides of the second resin part 2 were 15mm, 5mm, 4mm, and 2mm, respectively. Here, the main body of the injection-molded body is the first resin portion 1 (hereinafter, a portion corresponding to the "first resin portion 1" is also referred to as an "injection-molded body").

Evaluation of dimensional stability

Dimensional stability was evaluated by measuring the coefficient of linear expansion using the obtained injection-molded body. The linear expansion coefficient was measured by the following method using a thermomechanical analyzer (TMA/SS 6100 manufactured by SII nanotechnology co.

A test piece of 5X 10X 3(mm) was cut from the center of the injection molded article in the longitudinal direction. The test piece was placed in the above apparatus, and the temperature was raised from-20 ℃ to 130 ℃ at a rate of 5 ℃/min to remove the residual strain during molding. Thereafter, the test piece was placed again so as to be able to measure dimensional changes in the MD direction (the direction parallel to L2 in fig. 1) or the TD direction (the direction orthogonal to the MD direction in fig. 1, the direction parallel to L1) at the time of injection molding in the apparatus, and the dimensions at 23 ℃ were accurately measured. The temperature was raised from-20 ℃ to 80 ℃ at a temperature raising rate of 5 ℃/min, and the dimensional changes in the MD direction and TD direction during this period were measured. The dimensional change per unit length and unit temperature was obtained as the linear expansion coefficient. The smaller the value of the linear expansion coefficient, the better the dimensional stability. The average value of the linear expansion coefficient in the MD direction and the linear expansion coefficient in the TD direction (MDTD average linear expansion coefficient) is shown in table 1.

Evaluation of hinge resistance of weld portion

A test piece of 30X 150X 3(mm) was cut out from the center in the lateral direction of an injection-molded article described later. The short side portions at both ends of the test piece were fixed by using a bending tester (manufactured by Toyo Seiki Seisaku-Sho Ltd.), and the test piece was bent in the horizontal direction and then returned to a straight line shape, and then bent in the opposite direction and then returned to a straight line shape, and the number of times until the weld portion was broken was measured.

Production of injection-molded body for evaluating hinge resistance of weld portion

The obtained resin composition was injection-molded under the following conditions to produce an injection-molded article for evaluation shown in fig. 2. The resin composition melted in the injection molding machine is supplied into the mold cavity from two gates by the injection molding machine.

An injection molding machine: SE130DU (clamping force 130 ton, cylinder diameter 40mm) manufactured by Sumitomo heavy machinery industry Co., Ltd

The shape of the die cavity is as follows: 90mm (width) × 150mm (length) × 3mm (thickness)

Pouring: 2 gates located at the central parts of both sides of the 90mm side surface

Barrel temperature: 220 deg.C

Temperature of the die: 50 deg.C

Injection speed: 30 mm/sec

Cooling time: 30 seconds

Fig. 2 is a schematic view of an injection-molded body for evaluating the hinge resistance of a weld portion. The injection molded body 10 shown in fig. 2 has a first resin portion 1 corresponding to the mold shape, a second resin portion 2 corresponding to the gate shape, and a third resin portion 3 corresponding to the gate shape on the opposite side as well. First resin part 1 is a plate-shaped resin part having a width L1 of 90mm, a length L2 of 150mm, and a thickness (not shown) of 3 mm. In the injection-molded articles formed in the present and comparative examples, the lengths L3, L4 and the thicknesses (not shown) of the sides of second resin part 2 were 5mm, 2mm and 3mm, respectively. The length of each side of the third resin portion 3 is the same as that of the second resin portion 2. Here, the main body of the injection-molded body is the first resin portion 1 (hereinafter, a portion corresponding to the "first resin portion 1" is also referred to as an "injection-molded body").

As is clear from Table 1, the MDTD average linear expansion coefficient of the molded articles of examples is low, and the dimensional stability is excellent. That is, it was confirmed that the propylene resin composition of the present invention can produce a molded article having excellent dimensional stability, and the molded article of the present invention has excellent dimensional stability. In addition, it is found that the molded article of the example has a large number of times until the weld portion is broken in the bending test, and the weld portion has excellent hinge resistance.

Description of the reference symbols

1 … … first resin part, 2 … … second resin part, 10 … … injection molded body.