JP2014172985A - Fiber-reinforced polypropylene-based resin composition for compact with ribs, and compact with ribs obtained by molding the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber-reinforced polypropylene-based resin composition for a compact with ribs, which has a good weld appearance and sunken rib appearance as well as high rigidity and impact strength; and a compact obtained by molding the same.SOLUTION: Provided is a fiber-reinforced polypropylene-based resin composition for a compact with ribs, comprising 40 to 99 wt.% of a specific propylene-ethylene block copolymer (a) obtained by using a metallocene-based catalyst, and 1 to 60 wt.% of a specific fiber (b) (however, a total of (a) and (b) is 100 wt.%); and a compact with ribs obtained by molding the same.

Description

  The present invention relates to a fiber-reinforced polypropylene resin composition for a molded article with ribs and a molded article with ribs formed by molding the same, and more specifically, has a good weld appearance and rib sink appearance, and has high rigidity and high impact strength. The present invention relates to a certain fiber-reinforced polypropylene resin composition for a molded article with ribs and a molded article with ribs formed by molding the same.

The field of use of polypropylene resin compositions is expanding as a resin material having excellent physical properties, moldability, recyclability, economy, and the like. In particular, in the field of automobile parts such as instrument panels and pillars, and electrical equipment parts such as televisions and vacuum cleaners, polypropylene resin, and composite polypropylene in which polypropylene resin is reinforced with a filler such as glass fiber and elastomer (rubber). Polypropylene resin compositions such as resin are excellent in moldability, physical property balance, recyclability and economy, and are therefore widely used in various applications including molded articles.
In these fields, demands for higher functionality, larger size, diversification and complexity of applications of molded products of polypropylene resin compositions are increasing. When trying to secure high strength, especially with large molded bodies, it is one of the common methods to try to obtain a reinforcing effect by attaching ribs. It tends to be complicated. Especially in the automotive interior parts field, etc., in order to respond to high quality, it is represented by polypropylene resin composition and its molded product's moldability, balance of physical properties in mechanical properties, weld appearance and rib sink appearance. There is a need to improve the appearance. In particular, the surface quality of a molded body that is in close contact with human eyes, such as automobile interior parts, is extremely important. That is, the advancement of the quality can improve the texture of the molded body and give a higher-class feeling.

  In these various molded products, for the purpose of ensuring strong strength, fillers such as glass fibers and talc are contained in the polypropylene resin composition and the molded product thereof, and the rigidity (strength) of the resin composition and the molded product is included. It is widely done to improve. However, when a molded body is formed using a polypropylene-based resin composition containing such a filler, it contributes to the improvement of the mechanical properties of the molded body, but the moldability is reduced, and various appearance evaluations such as a weld appearance are performed. It is generally well known that it is rather negative.

  For example, in Patent Document 1, as a high-strength and high-rigidity polyolefin-based resin composition having mechanical strength comparable to that of a polyamide-based resin reinforced with glass fiber, (A) polypropylene obtained by sequential polymerization of two or more stages A polypropylene resin mixture in which the average dispersed particle size of the ethylene-propylene copolymer rubber in the mixture is 2 μm or less, and (B) a polyolefin resin (C) and a component (A), The filler having an average diameter of 0.01 to 1000 μm and an average aspect ratio (length / diameter) of 5 to 2500 with respect to 100 parts by weight of the total amount of component (B) is 0.1 to 200 parts by weight. A high-strength and high-rigidity polyolefin-based thermoplastic resin composition is disclosed. Although it is described that the molded product of the composition has high tensile strength and bending strength, the weld appearance and rib sink appearance of the molded product are not described and no consideration is given.

Patent Document 2 discloses (A) a polypropylene-based polymer and / or polyethylene having a density of 0.94 g / cm ³ or more as a composition imparted with high rigidity and bending rigidity without deteriorating dimensional stability. 75 to 98% by weight, (B) 2 to 25% by weight of a specific ethylene (co) polymer, 100 parts by weight of the above (A) + (B), and (C) 5 to 45 parts by weight of a fibrous inorganic filler There is disclosed a fibrous inorganic filler-containing resin composition containing Although it is described that the composition exhibits high tensile strength and flexural modulus, the weld appearance and rib sink appearance of the molded article are not described and no consideration is given.

  On the other hand, automobile parts made of a polypropylene resin composition for ribbed molded bodies are often molded by injection molding from the viewpoint of productivity. However, in injection molding, a rib sink appearance defect may occur. In order to eliminate these appearance defects, painting or the like is performed as necessary. As a result, the manufacturing process of the automobile parts becomes complicated and the cost is likely to increase. As a material having excellent molding appearance, for example, in Patent Document 3, (A) 40 to 99 parts by weight of a propylene-based block copolymer produced using a specific catalyst, (B) 0 to 35 parts by weight of an elastomer (E) The propylene-type resin composition which consists of 1-40 weight part of fillers is disclosed. The composition and its molded product are described as having good molded appearance, good rigidity, and high fluidity during injection molding, but there is no description of rib sink appearance, and no consideration is given. Not.

JP 2002-003691 A JP 7-048481 A JP 2011-132294 A

  An object of the present invention is to provide a molded article with a rib that has a good weld appearance of a molded product, particularly a good rib sink appearance, and has high rigidity and high impact strength in view of the above-mentioned problems of the prior art. An object of the present invention is to provide a fiber-reinforced polypropylene resin composition and a molded body with ribs formed by molding the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that specific propylene-ethylene block copolymers, fiber materials, and specific modified polyolefins and thermoplastic elastomers as components preferably used. And a fiber-reinforced propylene-based resin composition for a molded article with ribs formed by blending at least one selected from the group consisting of fatty acid amides at a specific ratio, or a molded article with ribs formed by molding the above-mentioned problems The present inventors have found that the problem can be solved, and have completed the present invention based on these findings.

That is, according to the first invention of the present invention, the following propylene-ethylene block copolymer (A) 40 wt% to 99 wt% and fiber (A) 1 wt% to 60 wt% (provided that (A ) And (A) is 100% by weight). A fiber-reinforced polypropylene resin composition for a molded article with ribs is provided.
Propylene-ethylene block copolymer (a): having the requirements defined in the following (a-i) to (a-iv).
(A-i): Using a metallocene-based catalyst, 30% to 95% by weight of propylene alone or a propylene-ethylene random copolymer component (A-A) having an ethylene content of 7% by weight or less in the first step; By sequentially polymerizing 70 wt% to 5 wt% of a propylene-ethylene random copolymer component (A-B) containing 3 to 20 wt% more ethylene than the component (A-A) in two steps. (However, the total amount of (A-A) and (A-B) is 100% by weight).
(A-ii): Melting peak temperature (Tm) measured by DSC method is 110 ° C to 150 ° C.
(A-iii): In the temperature-loss tangent curve obtained by solid viscoelasticity measurement, the tan δ curve has a single peak at 0 ° C. or lower.
(A-IV): The melt flow rate (MFR: 230 ° C., 2.16 kg load) of the entire propylene-ethylene block copolymer (A) is 0.5 g / 10 min to 200 g / 10 min.
Fiber (A): It has the requirements specified in (I-i) below.
(Ii): At least one selected from the group consisting of glass fiber, carbon fiber and whisker.

  In addition, according to the second invention of the present invention, there is provided a fiber-reinforced polypropylene resin composition for a molded article with ribs, wherein the fiber (A) is a glass fiber in the first invention.

  Moreover, according to 3rd invention of this invention, in 2nd invention, the fiber reinforced polypropylene resin composition for rib-shaped molded objects whose length of the said glass fiber is 2 mm or more and 20 mm or less is provided.

According to the fourth invention of the present invention, in any one of the first to third inventions, the following modified polyolefin (c) is further added to 100 parts by weight of the total amount of (a) and (b). ) A molded article with ribs containing at least one selected from the group consisting of 0.01 to 10 parts by weight, thermoplastic elastomer (d) 1 to 30 parts by weight, and fatty acid amide (e) 0.01 to 3 parts by weight. A fiber-reinforced polypropylene resin composition is provided.
Modified polyolefin (c): It has the requirements specified in the following (ui).
(Ui): At least one selected from the group consisting of acid-modified polyolefin and hydroxy-modified polyolefin.
Thermoplastic elastomer (D): It has the requirements specified in the following (E-i) and (E-ii).
(D -i): a density of ^{0.86g / cm 3 ~0.92g / cm 3} .
(D-ii): Melt flow rate (230 ° C., 2.16 kg load) is 0.5 g / 10 min to 100 g / 10 min.
Fatty acid amide (e): having the requirements specified in (i) below.
(Oi): a fatty acid amide represented by the following formula (A).
RCONH2 Formula (A)
[In formula (A), R represents a C10-25 linear aliphatic hydrocarbon group. ]

  Moreover, according to 5th invention of this invention, the molded object with a rib formed by shape | molding the fiber reinforced polypropylene-type resin composition for molded objects with a rib of 1st-4th invention is provided.

  According to a sixth aspect of the present invention, in the fifth aspect, a ribbed molded body that is an automobile part is provided.

The fiber-reinforced polypropylene resin composition for a molded article with ribs of the present invention and the molded article with ribs formed by molding the same have good rib sink appearance, high rigidity and high impact strength.
Therefore, automotive interior and exterior such as instrument panels, glove boxes, console boxes, door trims, armrests, grip knobs, various trims, ceiling parts, housings, pillars, mudguards, bumpers, fenders, back doors, fan shrouds, etc. It can be suitably used for automobile parts such as engine room parts, electrical and electronic equipment parts such as TVs and vacuum cleaners, various industrial parts, housing equipment parts such as toilet seats, and building material parts.

FIG. 1 is a diagram showing the elution amount and elution amount integration by temperature rising elution fractionation (TREF).

The present invention relates to a specific propylene-ethylene block copolymer (a) (hereinafter also simply referred to as component (a)) of 40% by weight to 99% by weight and a specific fiber (a) (hereinafter simply referred to as component (a). 1) to 60% by weight (provided that the total amount of (a) and (b) is 100% by weight), and (a) and (b) Specific modified polyolefin (c) (hereinafter also referred to simply as component (c)) 0.01 to 10 parts by weight, thermoplastic elastomer (d) (hereinafter simply referred to as component (c) D) 1 to 30 parts by weight and fatty acid amide (e) (hereinafter also simply referred to as component (e)) 0.01 to 3 parts by weight, Reinforced polypropylene resin composition and ribbed composition formed by molding the same Body on.
The fiber-reinforced polypropylene resin composition for a ribbed molded body of the present invention and the ribbed molded body formed by molding the same eliminate the problems of the conventional polypropylene resin composition and the molded body, It is suitable for obtaining molded articles for automobile parts and the like. That is, the present invention provides a fiber-reinforced polypropylene resin composition for a molded article with ribs having good weld appearance and rib sink appearance and having high rigidity and high impact strength, and a molded article with ribs formed by molding the same. It is.

  Hereinafter, the fiber-reinforced polypropylene resin composition for a molded article with ribs of the present invention and the molded article with ribs formed by molding the same will be described in detail for each item.

I. Constituent components of fiber reinforced polypropylene resin composition for ribbed molded article 1. Propylene-ethylene block copolymer (A) (component (A))
The component (a) used in the present invention is a propylene-ethylene block copolymer having the requirements defined in the following (a-i) to (a-iv), and the fiber-reinforced polypropylene resin composition of the present invention. And a ribbed molded body formed by molding the same (hereinafter, also simply referred to as “fiber reinforced composition” and “molded body”), while maintaining high impact strength and improving the weld appearance in particular. Has features.
(A-i): Using a metallocene-based catalyst, 30% to 95% by weight of propylene alone or a propylene-ethylene random copolymer component (A-A) having an ethylene content of 7% by weight or less in the first step; By sequentially polymerizing 70 wt% to 5 wt% of a propylene-ethylene random copolymer component (A-B) containing 3 to 20 wt% more ethylene than the component (A-A) in two steps. (However, the total amount of (A-A) and (A-B) is 100% by weight).
(A-ii): Melting peak temperature (Tm) measured by DSC method is 110 ° C to 150 ° C.
(A-iii): In the temperature-loss tangent curve obtained by solid viscoelasticity measurement, the tan δ curve has a single peak at 0 ° C. or lower.
(A-IV): The melt flow rate (MFR: 230 ° C., 2.16 kg load) of the entire propylene-ethylene block copolymer (A) is 0.5 g / 10 min to 200 g / 10 min.

The propylene-ethylene block copolymer here is also referred to as propylene alone or a propylene-ethylene random copolymer component (A-A) having an ethylene content of 7% by weight or less (hereinafter also referred to as component (A-A)). And propylene-ethylene random copolymer component (A-B) (hereinafter also referred to as component (A-B)) containing 3 to 20% more ethylene than the component (A-A). ) Are obtained by sequential polymerization, and are generally called “block copolymers”, and the component (A-A) and the component (A-B) are not necessarily completely combined in a block form. It doesn't have to be a thing.
Moreover, 2 or more types can also be used together for a component (a).

(1) Each requirement (a-i)
The component (a) used in the present invention is a propylene alone or an ethylene content of 7 wt% or less, preferably 5 wt% or less, more preferably 3 wt% in the first step using the metallocene catalyst as described above. 30% to 95% by weight of the following propylene-ethylene random copolymer component (A-A), preferably 3% to 20% by weight more ethylene than the component (A-A) in the second step, 6 to 18% by weight of ethylene, more preferably 8 to 16% by weight of ethylene, and a propylene-ethylene random copolymer component (A-B) containing 70 to 5% by weight. % Sequential polymerization is required.
Here, if the difference in ethylene content between the second step component (A-B) and the first step component (A-A) is within the range defined in the present invention, the fiber-reinforced composition of the present invention is good. While maintaining high impact strength, it is possible to achieve a good weld appearance. That is, when the difference in ethylene content between the second step component (A-B) and the first step component (A-A) is less than 3% by weight, the impact strength of the fiber-reinforced composition and the molded body of the present invention is low. May decrease. On the other hand, when it exceeds 20% by weight, the compatibility between the component (A-A) and the component (A-B) is lowered, and the weld appearance may be deteriorated.

  That is, in the component (a), sequential polymerization of components having different ethylene contents within a predetermined range in the first step and the second step kept high impact strength in the fiber reinforced composition and molded product of the present invention. Above, after polymerizing the component (A-A), in order to develop a good weld appearance, and to prevent problems such as adhesion of reaction products to the reactor, It is necessary to use a method of polymerizing the component (A-B). In the present application, the ethylene content is determined by the method described in Examples below.

(A-ii) Melting peak temperature (Tm) The melting peak temperature (Tm) measured by the DSC (Differential Scanning Calorimetry) method of the component (a) used in the present invention is in the range of 110 ° C to 150 ° C. It is necessary to be, preferably 115 to 148 ° C, more preferably 120 to 145 ° C. Since the Tm measured by the DSC (Differential Scanning Calorimetry) method of the component (a) used in the present invention is within the specified range of the present invention, the resin composition and molded product of the present invention have high impact strength and high strength. It becomes possible to achieve both rigidity. That is, if Tm is less than 110 ° C., the rigidity of the fiber reinforced composition and the molded body of the present invention may be lowered. On the other hand, if it exceeds 150 ° C., impact strength and the like may be reduced. In the present application, the melting peak temperature (Tm) is obtained by using a differential scanning calorimeter (for example, DSC6200 manufactured by Seiko Instruments Inc. in the present application), taking 5.0 mg of sample, holding at 200 ° C. for 5 minutes, It is measured by a method of crystallization to 10 ° C. at a temperature lowering speed of 10 ° C./min and further melting at a temperature rising speed of 10 ° C./min.

(A-iii) Peak temperature of tan δ curve in temperature-loss tangent curve Component (a) used in the present invention is a temperature-loss tangent curve obtained by solid viscoelasticity measurement (DMA). It is necessary to have a single peak below.
That is, in the fiber reinforced composition and the molded body of the present invention, in order to express various mechanical properties, particularly high impact strength, component (A) and component (A-B) in component (A) Is not phase-separated, in which case the tan δ curve shows a single peak below 0 ° C.
On the other hand, when the component (A-A) and the component (A-B) are in a phase separation structure, the glass transition temperature of the amorphous part contained in the component (A-A) and the component (A-B) Since the glass transition temperature of the amorphous part contained in each is different, there are a plurality of peaks indicated by the tan δ curve.
In the present invention, solid viscoelasticity measurement (DMA) is specifically performed by applying a sinusoidal strain of a specific frequency to a strip-shaped sample piece and detecting the generated stress. The frequency is 1 Hz, and the measurement temperature is raised stepwise from −60 ° C. until the sample is melted and cannot be measured.
Further, it is recommended that the magnitude of the strain is about 0.1% to 0.5%. From the obtained stress, the storage elastic modulus G ′ and the loss elastic modulus G ″ are obtained by a known method, and the loss tangent (= loss elastic modulus / storage elastic modulus) defined by this ratio is plotted against the temperature. The component (a) shows a sharp peak in the temperature range of 0 ° C. or lower, and generally the peak of the tan δ curve at 0 ° C. or lower observes the glass transition of the amorphous part. It is a glass transition temperature Tg (° C.).

Specifically, the solid viscoelasticity measurement (DMA) used in the present invention is as follows, and can also be measured using an equivalent apparatus or the like.
The sample used is a 10 mm width × 18 mm length × 2 mm thickness strip cut out from a 2 mm thick sheet formed by injection molding under the following conditions.
The apparatus uses ARES manufactured by Rheometric Scientific.
Standard number: JIS-7152 (ISO294-1)
Frequency: 1Hz
Measurement temperature: From -60 ° C. until the sample melts.
Strain: Range of 0.1 to 0.5% Molding machine: TU-15 injection molding machine manufactured by Toyo Machine Metal Co., Ltd. Molding machine set temperature: 80, 80, 160, 200, 200, 200 ° C. from below the hopper
Mold temperature: 40 ℃
Injection speed: 200 mm / sec (speed in the mold cavity)
Injection pressure: 800 kgf / cm ²
Holding pressure: 800 kgf / cm ²
Holding time: 40 seconds
Mold shape: Flat plate (2mm thickness, 30mm width, 90mm length)

(A-iv) Melt flow rate (MFR) The total melt flow rate (MFR: 230 ° C., 2.16 kg load) of the component (a) used in the present invention is 0.5 g / 10 min to 200 g / 10 min. It is necessary to be in the range of 3 g / 10 min to 150 g / 10 min, more preferably 5 g / 10 min to 50 g / 10 min. By setting the melt flow rate of the entire component (a) used in the present invention within the range specified in the present invention, the fiber reinforced composition of the present invention has all good moldability, good weld appearance, and high impact strength. Can be achieved. That is, when the MFR is less than 0.5 g / 10 minutes, not only the weld appearance but also the moldability may be deteriorated in the fiber reinforced composition and the molded body of the present invention. On the other hand, if it exceeds 200 g / 10 minutes, the impact strength may decrease. The MFR can be adjusted by adjusting polymerization conditions (polymerization temperature, comonomer amount, hydrogenation amount, etc.) described later, or using a molecular weight depressant.
In addition, the melt flow rate in this specification is the value measured based on A method of JISK7210: 1999, condition M (230 degreeC, 2.16kg load), and a unit is g / 10min.

(2) Production method (i) Metallocene catalyst The production of component (a) used in the present invention requires the use of a metallocene catalyst.
The type of the metallocene catalyst is not particularly limited as long as the component (a) having the performance of the present invention can be produced, but in order to satisfy the requirements of the present invention, for example, the components as shown below It is preferable to use a metallocene catalyst comprising (a), (b), and component (c) used as necessary.
Component (a): at least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula (1).
Component (b): at least one solid component selected from the following (b-1) to (b-4).
(B-1): A particulate carrier on which an organic aluminum oxy compound is supported.
(B-2): A particulate carrier carrying an ionic compound or Lewis acid capable of reacting with component (a) to convert component (a) into a cation.
(B-3): Solid acid fine particles.
(B-4): Ion exchange layered silicate.
Component (c): an organoaluminum compound.

As the component (a), at least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula (1) can be used.
^{_{Q (C 5 H 4-a}} R 1 a) (C 5 H 4-b R 2 b) MeXY (1)
[Wherein Q represents a divalent binding group that bridges two conjugated five-membered ring ligands, Me represents a metal atom selected from titanium, zirconium, and hafnium, X and Y represent a hydrogen atom, A halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group is shown, and X and Y may be the same or different from each other. R1 and R2 each represent hydrogen, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a boron-containing hydrocarbon group, or a phosphorus-containing hydrocarbon group. . a and b are the number of substituents. ]

  Among them, preferred for the production of the component (a) is a substituted cyclopentadienyl group, a substituted indenyl group, a substituted fluorenyl group crosslinked with a silylene group, a germylene group or an alkylene group having a hydrocarbon substituent as Q. A transition metal compound comprising a ligand having a substituted azulenyl group, particularly preferably a silylene group having a hydrocarbon substituent or a 2,4-position substituted indenyl group bridged by a germylene group, 2,4 Examples thereof include transition metal compounds composed of a ligand having a -position-substituted azulenyl group.

As the component (b), at least one solid component selected from the aforementioned components (b-1) to (b-4) is used. Each of these components is a well-known thing, and can be used selecting it suitably from well-known techniques. Specific examples and manufacturing methods thereof are described in detail in JP-A No. 2002-284808, JP-A No. 2002-53609, JP-A No. 2002-69116, JP-A No. 2003-105015, and the like.
Of the component (b), particularly preferred is the ion-exchange layered silicate of component (b-4), and more preferred are chemical treatments such as acid treatment, alkali treatment, salt treatment, and organic matter treatment. Is an ion-exchange layered silicate.

Examples of the organoaluminum compound used as the component (c) as necessary include the following general formula (2)
AlRaP _3-a (2)
(Wherein R represents a hydrocarbon group having 1 to 20 carbon atoms, P represents hydrogen, halogen or alkoxy group, a represents a number of 0 <a ≦ 3), trimethylaluminum, Trialkylaluminum such as tripropylaluminum and triisobutylaluminum or halogen- or alkoxy-containing alkylaluminum such as diethylaluminum monochloride and diethylaluminum monomethoxide. In addition, aluminoxanes such as methylaluminoxane can also be used. Of these, trialkylaluminum is particularly preferred.

  As a method for forming the catalyst, the component (a), the component (b) and, if necessary, the component (c) are brought into contact with each other to form a catalyst. In addition, the contact method will not be specifically limited if it is a method which can form a catalyst, A well-known method can be used.

Moreover, the usage-amount of component (a), (b), and (c) is arbitrary. For example, the amount of component (a) used relative to component (b) is preferably in the range of 0.1 μmol to 1,000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of component (b). The amount of component (c) used relative to component (b) is preferably such that the amount of transition metal is 0.001 μmol to 100 μmol, particularly preferably 0.005 μmol to 50 μmol, relative to 1 g of component (b).
Furthermore, it is preferable that the catalyst used in the present invention is subjected to a prepolymerization treatment in which a small amount of polymer is brought into contact with an olefin in advance.

(Ii) Sequential Polymerization In producing the component (a) used in the present invention, it is necessary to sequentially polymerize the component (a-A) and the component (a-B).
When performing sequential polymerization, either a batch method or a continuous method can be used, but it is generally desirable to use a continuous method from the viewpoint of productivity.

In the case of the batch method, the component (A-A) and the component (A-B) can be polymerized even by using a single reactor by changing the polymerization conditions with time. As long as the effects of the present invention are not impaired, a plurality of reactors may be connected in parallel.
In the case of the continuous method, since it is necessary to polymerize the component (A-A) and the component (A-B) separately, it is necessary to use a production facility in which two or more reactors are connected in series. A plurality of reactors may be connected in series and / or in parallel for each of the component (A-A) and the component (A-B) as long as the effect is not inhibited.

(Iii) Polymerization process For the polymerization process of component (a), any polymerization method such as a slurry method, a bulk method, or a gas phase method can be used. Although it is possible to use supercritical conditions as intermediate conditions between the bulk method and the gas phase method, they are substantially equivalent to the gas phase method, and are therefore included in the gas phase method without particular distinction.
Since component (A-B) is easily soluble in organic solvents such as hydrocarbons and liquefied propylene, it is desirable to use a gas phase method for the production of component (A-B).
For the production of the component (A-A), there is no particular problem in using any process, but when producing the component (A-A) having relatively low crystallinity, the product to the reactor is used. It is desirable to use a vapor phase method in order to avoid problems such as adhesion.
Therefore, it is most desirable to first polymerize the component (A-A) by the bulk method or the gas phase method and then polymerize the component (A-B) by the gas phase method using the continuous method.

(Iv) Other polymerization conditions The polymerization temperature can be used without any particular problem as long as it is within a commonly used temperature range. Specifically, a range of 0 ° C. to 200 ° C., more preferably 40 ° C. to 100 ° C. can be used.
The polymerization pressure varies depending on the process to be selected, but the optimum pressure can be used without any problem as long as it is in a pressure range usually used. Specifically, the relative pressure with respect to atmospheric pressure can be greater than 0 MPa and up to 200 MPa, more preferably in the range of 0.1 MPa to 50 MPa. At this time, an inert gas such as nitrogen may coexist.
When the sequential polymerization of the component (A-A) in the first step and the component (A-B) in the second step is performed, it is desirable to add a polymerization inhibitor into the system in the second step. When a polymerization inhibitor is added to the reactor in which ethylene-propylene random copolymerization in the second step is performed, product quality such as particle properties (fluidity, etc.) and gel of the resulting powder can be improved. Various techniques have been studied for this method, and examples thereof include the methods described in Japanese Patent Publication Nos. 63-54296, 7-25960, and 2003-2939. It is desirable to apply the method to the present invention.
As the component (a) obtained by the action of the metallocene catalyst, a commercially available product can be used. For example, the Wellnex series manufactured by Nippon Polypro Co., Ltd. can be suitably used.

(3) Blending ratio The blending amount of the component (a) used in the present invention is 40% to 99% by weight, preferably 45%, in the total amount of 100% by weight of the component (a) and the component (a). % By weight to 95% by weight, more preferably 48 to 90% by weight, particularly preferably 50% to 85% by weight. By setting the blending amount of the component (a) in such a range, it is possible to achieve a good weld appearance and rib sink appearance while maintaining high impact strength and rigidity. That is, when the blending amount of the component (a) is less than 40% by weight, the impact strength of the fiber reinforced composition and the molded product of the present invention may be lowered, or the weld appearance may be deteriorated. On the other hand, if it exceeds 99% by weight, the rigidity may be lowered, or the rib sink appearance may be deteriorated.

2. Fiber (I) (Ingredient (I))
The component (I) used in the present invention is at least one fiber (fibrous filler) selected from the group consisting of glass fiber, carbon fiber and whisker. Component (A) is combined with the component (A) having a low melting point polymerized by a metallocene catalyst to improve physical properties such as rigidity and impact strength of the fiber reinforced composition and molded article of the present invention, and to improve rib sink appearance. There is an effect of contributing.

(1) Kind, Production Component (A) is at least one fiber selected from glass fiber, carbon fiber and whisker as described above. In addition, the effects of the present invention can be sufficiently obtained, and glass fibers are preferably used from the viewpoints of easiness of production of the fiber-reinforced polypropylene resin composition for a molded article with ribs of the present invention and economic efficiency.
In order to further improve the effect of the present invention, two or more of these components (A) can be used in combination, and the components (A) and other optional resin components are previously added at a relatively high concentration. It can also be used in the form of a so-called master batch.
Moreover, various inorganic fillers such as talc, glass beads, glass balloons, mica and the like that do not correspond to the component (a) can be used in combination as long as the effects of the present invention are not significantly impaired.
Hereinafter, the various fibers defined in (ii) in the present invention will be described in detail.

(I) Glass fiber In this invention, it can use without being specifically limited as glass fiber, As a kind of glass used for a fiber, E glass, C glass, A glass, S glass, etc. are mentioned, for example. Among them, E glass is preferable. The manufacturing method of this glass fiber is not specifically limited, It manufactures with a well-known various manufacturing method.
Two or more types of glass fibers can be used in combination.

The fiber diameter of the glass fiber is preferably 3 μm to 25 μm, more preferably 6 μm to 20 μm. The fiber diameter is obtained by cutting the fiber perpendicularly to the fiber length direction, measuring the diameter by observing the cross section under a microscope, and calculating the average value of the diameters of 100 or more fibers.
When the fiber diameter is less than 3 μm, the glass fiber may be easily broken during the production and molding of the fiber reinforced composition of the present invention and the molded body. On the other hand, when the fiber diameter exceeds 25 μm, the aspect ratio of the fiber decreases. As a result, the effects of improving the rigidity and impact strength of the fiber reinforced composition and the molded product of the present invention may be reduced.
The fiber length is preferably 2 mm to 20 mm, more preferably 3 to 10 mm, although it depends on the glass fiber used. If it is less than 2 mm, the physical properties such as rigidity and impact strength of the fiber reinforced composition and the molded product of the present invention may be reduced. On the other hand, if it exceeds 20 mm, the weld appearance and rib sink appearance may be deteriorated.

In addition, the fiber length in this case represents the length in the case of using the fiber before melt-kneading as a raw material as it is, when it is a normal roving-like or strand-like fiber. However, this is not the case in the case of glass fiber-containing pellets in which a large number of continuous glass fibers are integrated by melt extrusion, which will be described later, and the length of one side (extrusion direction) of the pellet is substantially equal to the pellet. Since it is the same as the length of the inside fiber, the length of one side (extrusion direction) of the pellet is defined as the fiber length.
Here, “substantially” specifically refers to the length of the glass fiber-containing pellet when the length is 50% or more, preferably 90% or more, based on the total number of fibers in the fiber-containing pellet. It is the same as (extrusion direction) and means that the fiber is hardly broken during the pellet preparation.
In addition, in this specification, fiber length is calculated | required by measuring with a microscope and calculating the average value of the length of 100 or more fibers.
For example, when the fiber (I) is a glass fiber, the glass fiber is mixed with a surfactant-containing water, and the mixed water solution is dropped and diffused on a thin glass plate. According to a method of measuring the length of 100 or more glass fibers using a VHX-900 type) and calculating the average value.

In the present invention, the glass fiber can be either surface-treated or untreated, but for improving dispersibility in the component (a), an organic silane coupling agent, a titanate cup, etc. It is preferable to use one that has been surface-treated with a ring agent, an aluminate coupling agent, a zirconate coupling agent, a silicone compound, a higher fatty acid, a fatty acid metal salt, a fatty acid ester, or the like.
Examples of the organic silane coupling agent used for the surface treatment include vinyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and 3-acryloxypropyl. And trimethoxysilane. Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, and isopropyl tri (N-aminoethyl) titanate. Moreover, as an aluminate coupling agent, acetoalkoxy aluminum diisopropylate etc. can be mentioned, for example. Examples of the zirconate coupling agent include tetra (2,2-diallyloxymethyl) butyl, di (tridecyl) phosphitozirconate; neopentyl (diallyl) oxy, and trineodecanoyl zirconate. Examples of the silicone compound include silicone oil and silicone resin.

Furthermore, examples of the higher fatty acid used for the surface treatment include oleic acid, capric acid, lauric acid, palmitic acid, stearic acid, montanic acid, kaleic acid, linoleic acid, rosin acid, linolenic acid, undecanoic acid, and undecenoic acid. Is mentioned. Examples of the higher fatty acid metal salt include fatty acids having 9 or more carbon atoms, such as sodium salts such as stearic acid and montanic acid, lithium salts, calcium salts, magnesium salts, zinc salts, and aluminum salts. Of these, calcium stearate, aluminum stearate, calcium montanate, and sodium montanate are preferred. Examples of fatty acid esters include polyhydric alcohol fatty acid esters such as glycerin fatty acid esters, alpha sulfone fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, polyethylene fatty acid esters, and sucrose fatty acid esters.
The amount of the surface treatment agent used is not particularly limited, but is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the glass fiber. .

Further, the glass fiber may be used that has been focused (surface) treated with a sizing agent, and the types of sizing agent include epoxy sizing agents, aromatic urethane sizing agents, aliphatic urethane sizing agents, Examples thereof include acrylic sizing agents and maleic anhydride-modified polyolefin sizing agents.
Since these sizing agents need to be melted in the melt-kneading with the polypropylene resin, it is preferable that they are melted at 200 ° C. or lower.

The glass fiber can also be used as a so-called chopped strand glass fiber obtained by cutting a fiber yarn into a desired length. It is preferable to use this chopped strand glass fiber in order to further enhance the effects of improving the rigidity and impact strength of the fiber reinforced composition and the molded body of the present invention.
Specific examples of the glass fiber include Nippon Electric Glass Co., Ltd. (T480H).

In addition, these glass fibers are formed into pellets in which an arbitrary amount of an arbitrary resin component such as component (a) or component (c) and a large number of continuous glass fibers are integrated by melt extrusion. In addition, the glass fiber length in the pellet may be substantially the same as the length of one side (extrusion direction) of the pellet, and may be used as a “glass fiber-containing pellet”. It is preferable from the viewpoints of further improving physical properties such as the rigidity and impact strength of the fiber reinforced composition and the molded body. In this case, “substantially” means that, as described above, the glass fiber length in the glass fiber-containing pellet is the same as the length (extrusion direction) of the glass fiber-containing pellet. It means that the fiber is hardly broken.
The method for producing such glass fiber-containing pellets is not particularly limited. For example, while using a resin extruder, a plurality of continuous glass fibers are drawn from a fiber rack through a crosshead die, for example, an arbitrary amount of components ( It is preferable to manufacture by a method (pultrusion molding) in which a large number of glass fibers are assembled and integrated by melt extrusion (impregnation) of a resin such as a) in a molten state, since the fibers are hardly broken.

As described above, the length (extrusion direction) of the glass fiber-containing pellet is preferably 2 mm to 20 mm.
Moreover, in this glass fiber containing pellet, it is preferable that content of glass fiber is 20 weight%-70 weight% on the basis of 100 weight% of this whole pellet.
When glass fiber-containing pellets having a glass fiber content of less than 20% by weight are used in the present invention, physical properties such as rigidity and impact strength of the fiber reinforced composition and the molded article may be lowered, whereas 70% by weight. In the case where the content is more than%, the weld appearance and rib sink appearance may be deteriorated.

(Ii) Carbon fiber The carbon fiber used in the present invention is not particularly limited, and for example, ultrafine fibers having a fiber diameter of 500 nm or less, which are also referred to as fine carbon fibers, can be used.
The fiber diameter of the carbon fiber is preferably 2 μm to 20 μm, and more preferably 3 μm to 15 μm. When the fiber diameter is less than 2 μm, the carbon fiber may be easily broken during the production and molding of the fiber reinforced composition and molded body of the present invention. There is a possibility that the effect of improving physical properties such as impact strength may be reduced. In addition, when the fiber diameter exceeds 20 μm, the fiber aspect ratio decreases, and the effects of improving the rigidity and impact strength of the fiber reinforced composition and the molded body of the present invention may decrease.
Here, the measuring method of a fiber diameter is a well-known method, for example, JIS R7607 (old JIS R7601) and a microscope observation method are mentioned.
Further, the fiber length of the carbon fiber is preferably 1 mm to 20 mm, and more preferably 3 mm to 10 mm. In addition, the fiber length in this case represents the length in the case of using carbon fiber as a raw material as it is. However, the case of “carbon fiber-containing pellets” in which a large number of continuous carbon fibers are integrated by melt extrusion is not limited to this, and is the same as glass fiber-containing pellets as described later.
When the fiber length is less than 1 mm, the final fiber length after molding of the fiber reinforced composition and the molded body of the present invention becomes shorter, and physical properties such as rigidity and impact strength of the fiber reinforced composition and the molded body of the present invention are reduced. On the other hand, if it exceeds 20 mm, the weld appearance and rib sink appearance may be deteriorated. Two or more types of carbon fibers can be used in combination.

The type of carbon fiber is not particularly limited as described above. For example, PAN (polyacrylonitrile) carbon fiber mainly composed of acrylonitrile, pitch carbon fiber mainly composed of tar pitch, and rayon carbon fiber. Etc., and all are preferably used. Although these are highly suitable for the present invention, PAN-based carbon fibers are preferred from the viewpoints of composition purity and uniformity. These may be used alone or in combination. In addition, the manufacturing method of these carbon fibers is not specifically limited.
As specific examples of carbon fiber, in PAN-based carbon fiber, trade name "Pyrofil" manufactured by Mitsubishi Rayon Co., Ltd., trade name "Torayca" manufactured by Toray Industries, Inc., trade name "Beth Fight" manufactured by Toho Tenax Co., etc. Examples of the pitch-based carbon fiber include a product name “DIALEAD” manufactured by Mitsubishi Plastics, a product name “DonaCarbo” manufactured by Osaka Gas Chemicals, and a product name “Kureka” manufactured by Kureha Chemicals.

Carbon fibers usually have a tensile elastic modulus of about 200 GPa to 1000 GPa, but in the present invention from the strength and economics of the fiber reinforced composition of the present invention and the molded body, it is preferable to use those of 200 GPa to 900 GPa. It is more preferable to use 200 GPa to 300 GPa.
Further, the carbon fiber has a density of usually about ^{1.7g / cm 3 ~5g / cm 3} , having a density of 1.7g ^/ cm ³ ~2.5g ^/ cm 3 and the like lightweight and economy Is preferably used.
Here, the tensile modulus and density are measured by known methods. For example, the tensile modulus can be JIS R7606 (former JIS R7601), and the density can be JIS R7603 (former JIS R7601). Can be mentioned.

These carbon fibers can be used as so-called chopped (strand-like) carbon fibers (hereinafter also simply referred to as CCF) obtained by cutting the fiber yarn into a desired length, and various sizing agents can be used as necessary. It is also possible to use a focusing process. In the present invention, it is preferable to use this CCF in order to further enhance each effect of improving physical properties such as rib sink appearance and rigidity / impact strength in the fiber reinforced composition and molded body of the present invention.
As specific examples of such CCF, in the case of PAN-based carbon fiber, the product name “Pyrofil Chop” manufactured by Mitsubishi Rayon Co., Ltd., the product name “Torayca Chop” manufactured by Toray Industries, Inc., the product name “Besfight Chop” manufactured by Toho Tenax Co., Ltd., etc. For pitch-based carbon fiber, the product name “Dialead Chopped Fiber” manufactured by Mitsubishi Plastics Co., Ltd., the product name “Donna Carbo Chop” manufactured by Osaka Gas Chemical Company, and the product name “Kureka Chop” manufactured by Kureha Chemical Co., Ltd. Can be mentioned.

  These carbon fibers are preliminarily formed into pellets obtained by assembling and integrating an arbitrary amount of resin such as component (a) and component (c), and a number of continuous carbon fibers by melt extrusion processing, and The carbon fiber length in the pellet is substantially the same as the length of one side (extrusion direction) of the pellet, and is used as a “carbon fiber-containing pellet”. It is more preferable from the viewpoint of improving physical properties such as rigidity and impact strength. In addition, about the manufacturing method and each characteristic of this carbon fiber containing pellet, it is the same as that of the said glass fiber containing pellet.

(Iii) Whisker Whisker used in the present invention can be used without any particular limitation. Specific examples thereof include basic magnesium sulfate fiber (magnesium oxysulfate fiber), potassium titanate fiber, boron Examples include aluminum oxide fibers, calcium silicate fibers, and calcium carbonate fibers. Among them, basic magnesium sulfate fibers (magnesium oxysulfate fibers), potassium titanate fibers, and calcium carbonate fibers are preferable, and basic magnesium sulfate fibers ( Magnesium oxysulfate fiber) is particularly preferred.
The fiber diameter of the whisker is not particularly limited, but is preferably 1 μm or less in order to improve the rigidity and impact strength. The fiber length is not particularly limited, but is preferably 0.1 μm to 100 μm, more preferably 0.5 μm to 50 μm, and particularly preferably 1 μm to 20 μm in order to improve the rigidity and impact strength.
If the fiber diameter exceeds 1 μm, the aspect ratio of the fiber decreases, and in the fiber reinforced composition and the molded body of the present invention, the effect of improving the rigidity / impact strength may be likely to occur. The measuring method of a fiber diameter is a well-known method, for example, a microscope observation method is mentioned. In addition, 2 or more types of whiskers can be used in combination.

The manufacturing method of a whisker is not specifically limited, It manufactures with a well-known various manufacturing method. For example, in the case of basic magnesium sulfate fiber, it is produced by a method such as hydrothermal synthesis using magnesium hydroxide and magnesium sulfate as raw materials.
Whisker is generally finely powdered, but it can be used in the form of compacted or granulated or granulated products produced for the purpose of improving mixing workability. Good.
These whiskers are used for various surface treatments such as an organic titanate coupling agent, an organic silane coupling agent, an unsaturated carboxylic acid for the purpose of improving adhesiveness or dispersibility with the component (a). A surface treated with a modified polyolefin grafted with an acid or its anhydride, a fatty acid, a fatty acid metal salt, a fatty acid ester, or the like may be used.
Various products of such whiskers are commercially available from many companies, and a desired product can be purchased and used. Examples of such products include “Moss Heidi” manufactured by Ube Materials Corporation.

(2) Compounding ratio The compounding amount of the component (a) used in the present invention is 1% by weight to 60% by weight, preferably 5% in the total amount of the component (a) and the component (a) of 100% by weight. % By weight to 55% by weight, more preferably 10% to 52% by weight, still more preferably 15 to 50% by weight. By setting the blending amount of the component (a) in such a range, it is possible to achieve a good weld appearance and rib sink appearance while maintaining high impact strength and rigidity. That is, when the amount of component (I) is less than 1% by weight, the fiber reinforced composition of the present invention, the rigidity of the molded article and the rib sink appearance may be lowered. On the other hand, if it exceeds 60% by weight, physical properties such as weld appearance and impact strength may be deteriorated.
Here, the compounding amount of the component (a) is an actual amount. For example, when the glass fiber-containing pellet or the carbon fiber-containing pellet is used, the amount is calculated based on the actual content of the component (a) contained in the pellet. .

3. Ingredient (U): Modified polyolefin (U)
The component (c) used in the present invention is at least one selected from the group consisting of acid-modified polyolefins and hydroxy-modified polyolefins. Since component (c) can improve the interfacial strength between component (a) and component (a), by using component (c), the fiber reinforced composition and molded body of the present invention can be rigid.・ Higher physical properties such as impact strength can be imparted.

(1) Kind and Production In the present invention, the acid-modified polyolefin used as the component (c) is not particularly limited, and conventionally known ones can be used.
Examples of the acid-modified polyolefin include polyethylene, polypropylene, ethylene-α-olefin copolymer, ethylene-α-olefin-nonconjugated diene compound copolymer (EPDM, etc.), ethylene-aromatic monovinyl compound-conjugated diene compound copolymer. A polyolefin such as rubber is modified by graft copolymerization with an unsaturated carboxylic acid such as maleic acid or maleic anhydride. This graft copolymerization is performed, for example, by reacting the polyolefin with an unsaturated carboxylic acid in a suitable solvent using a radical generator such as benzoyl peroxide. Moreover, the component of unsaturated carboxylic acid or its derivative can also be introduce | transduced in a polymer chain by random or block copolymerization with the monomer for polyolefin.

Examples of unsaturated carboxylic acids used for modification include carboxyl groups such as maleic acid, fumaric acid, itaconic acid, acrylic acid, and methacrylic acid, and functional groups such as hydroxyl groups and amino groups as necessary. And a compound having a polymerizable double bond.
Examples of unsaturated carboxylic acid derivatives include acid anhydrides, esters, amides, imides, metal salts, and the like. Specific examples thereof include maleic anhydride, itaconic anhydride, methyl acrylate, and ethyl acrylate. , Butyl acrylate, methyl methacrylate, ethyl methacrylate, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, fumaric acid monoamide , Maleimide, N-butylmaleimide, sodium methacrylate and the like. Maleic anhydride is preferred.

Examples of the graft reaction conditions include di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2, Dialkyl peroxides such as 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxyisopropylcarbonate, 2, Peroxyesters such as 5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexyne-3, diacyl peroxides such as benzoyl peroxide , Diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-di (hydro -Oxy) An organic peroxide such as hydroperoxide such as hexane is used in a molten state or solution at a temperature of about 80 to 300 ° C. using about 0.001 to 10 parts by weight with respect to 100 parts by weight of the polyolefin. The method of making it react in a state is mentioned.
The acid-modified amount of the acid-modified polyolefin (sometimes referred to as graft ratio) is not particularly limited, but the acid-modified amount is preferably 0.05 to 10% by weight, more preferably 0.07, in terms of maleic anhydride. ~ 5% by weight.
Preferable acid-modified polyolefin includes maleic anhydride-modified polypropylene from the viewpoint of the effect of the present invention.

Further, the hydroxy-modified polyolefin used as the component (c) in the present invention is a modified polyolefin containing a hydroxyl group, and any conventionally known one can be used without any particular limitation. The hydroxy-modified polyolefin may have a hydroxyl group at an appropriate site, for example, at the end of the main chain or at the side chain.
Examples of the olefin resin constituting the hydroxy-modified polyolefin include, for example, homo- or copolymers of α-olefins such as ethylene, propylene, butene, 4-methylpentene-1, hexene, octene, nonene, decene, dodecene, α -A copolymer of an olefin and a copolymerizable monomer can be exemplified.
Preferred hydroxy-modified polyolefins include hydroxy-modified polyethylene (eg, low density, medium density or high density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene, ethylene- (meth) acrylate copolymer, ethylene-acetic acid. Vinyl copolymers, etc.), hydroxy-modified polypropylene (eg, polypropylene homopolymers such as isotactic polypropylene), random copolymers of propylene and α-olefins (eg, ethylene, butene, hexane, etc.), propylene-α-olefins Examples thereof include a block copolymer) and hydroxy-modified poly (4-methylpentene-1). Examples of the monomer for introducing the reactive group include a monomer having a hydroxyl group (for example, allyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc.). It can be illustrated.
The amount of modification by the monomer having a hydroxyl group is 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the olefin resin. The average molecular weight of the hydroxy-modified polyolefin is not particularly limited. For example, in the case of a low molecular weight system, the hydroxy-modified polyolefin can be obtained by a method in which a conjugated diene monomer is polymerized by a known method such as anionic polymerization, and a polymer obtained by hydrolyzing it is hydrogenated.
These components (c) may be used in combination of two or more.

(2) Blending ratio The blending amount of the component (c) used in the present invention is preferably 0.01 to 10 parts by weight, more preferably 100 parts by weight of the total amount of (a) and (b). Is 0.1 to 7 parts by weight, more preferably 0.5 to 5 parts by weight, particularly preferably 1 to 3 parts by weight, and particularly preferably 1 to 2 parts by weight. By making content of a component (u) into such a range, it becomes possible to express the effect of this invention more effectively. That is, when the blending amount of the component (c) is 0.01 parts by weight or less, the effect of reinforcing the interfacial strength may not be sufficiently obtained. When the amount exceeds 10 parts by weight, the fiber-reinforced composition and molded article of the present invention The impact strength may be reduced.
Examples of the modified polyolefin resin that can be used in the present invention as the component (c) include commercially available products such as OREVAC series manufactured by Arkema Corporation and modic series manufactured by Mitsubishi Chemical Corporation. In addition, since various products are commercially available from many companies, a desired product can be selected, purchased, and used from them.

4). Ingredient (D): Thermoplastic elastomer (D)
The component (d) used in the present invention is a thermoplastic elastomer having the requirements specified in the following conditions (e-i) and (d-ii), and is selected from olefinic elastomers, styrene elastomers, etc. It does not fall under (a) or component (c). The fiber reinforced composition and the molded body of the present invention are characterized by further improving functions such as impact strength.
(D -i): a density of ^{0.86g / cm 3 ~0.92g / cm 3} .
(D-ii): MFR (230 ° C., 2.16 kg load) is 0.5 g / 10 min to 100 g / 10 min.

(1) Density of each requirement (d -i) density component used in the present invention (d) ^{is, 0.86g / cm 3 ~0.92g / cm} 3, preferably 0.865g ^/ cm 3 ~0.90g / cm ^3, more preferably in the range of ^{0.86g / cm 3 ~0.875g / cm 3} . When the density of the component (d) used in the present invention is in such a range, the effects of the present invention are more effectively expressed, and the impact strength and rib sink appearance are further improved. That is, when the density is less than 0.86 g / cm ^3, in a fiber-reinforced composition and molded article of the present invention, may Ribuhike appearance is deteriorated, and when it exceeds 0.92 g / cm ^3, reduction impact strength There is a risk.

(D-ii) Melt flow rate (MFR)
The MFR (230 ° C., 2.16 kg load) of the component (d) used in the present invention is in the range of 0.5 g / 10 min to 100 g / 10 min, preferably 1.5 g / 10 min to 50 g / 10. Min, more preferably in the range of 2 g / 10 min to 15 g / 10 min. When the MFR of the component (d) used in the present invention is within such a range, the effects of the present invention are more effectively expressed. That is, when the MFR is less than 0.5 g / 10 minutes, the fluidity may deteriorate during the production of the fiber reinforced composition of the present invention and the molded body thereof, and handling may be difficult. When it exceeds, there exists a possibility that the impact strength of the fiber reinforced composition of this invention and a molded object may fall.

(2) Types The components (d) used in the present invention are olefin elastomers and styrene elastomers. Examples of olefin elastomers include ethylene / propylene copolymer elastomers (EPR) and ethylene / butene copolymer. Ethylene / α-olefin copolymer elastomer such as united elastomer (EBR), ethylene / hexene copolymer elastomer (EHR), ethylene / octene copolymer elastomer (EOR); ethylene / propylene / ethylidene norbornene copolymer, ethylene -Ethylene / α-olefin / diene terpolymer elastomer such as propylene / butadiene copolymer and ethylene / propylene / isoprene copolymer.
Examples of the styrene elastomer include styrene / butadiene / styrene triblock copolymer elastomer (SBS), styrene / isoprene / styrene triblock copolymer elastomer (SIS), styrene-ethylene / butylene copolymer elastomer ( SEB), styrene-ethylene / propylene copolymer elastomer (SEP), styrene-ethylene / butylene-styrene copolymer elastomer (SEBS), styrene-ethylene / butylene-ethylene copolymer elastomer (SEBC), hydrogenated styrene / Butadiene elastomer (HSBR), Styrene-ethylene / propylene-styrene copolymer elastomer (SEPS), Styrene-ethylene / ethylene / propylene-styrene copolymer elastomer (SEEPS) , Styrene - butadiene butylene - styrene copolymer elastomer (SBBS) can be exemplified. Furthermore, hydrogenated polymer-based elastomers such as ethylene-ethylene / butylene-ethylene copolymer elastomer (CEBC) can also be mentioned.
Among these, when at least one selected from the group consisting of ethylene / octene copolymer elastomer (EOR), ethylene / butene copolymer elastomer (EBR) and ethylene / propylene copolymer elastomer is used, the fiber-reinforced composition of the present invention. In the article and the molded body, it is preferable from the viewpoint that the performance such as impact strength is more excellent and the economy is also excellent. In addition, this component (d) can also use 2 or more types together.

(3) Production method The component (d) used in the present invention is, for example, an olefin elastomer, an ethylene / α-olefin copolymer elastomer, an ethylene / α-olefin / diene terpolymer elastomer, It is produced by polymerizing each monomer in the presence of a catalyst. Examples of the catalyst include titanium compounds such as titanium halide, organoaluminum-magnesium complexes such as alkylaluminum-magnesium complexes, so-called Ziegler-type catalysts such as alkylaluminum and alkylaluminum chloride, and WO 91/04257 pamphlet. The metallocene compound catalyst can be used.
As the polymerization method, polymerization can be performed by applying a production process such as a gas phase fluidized bed method, a solution method, or a slurry method. In addition, among the components (d), the styrene elastomer can be produced by a normal anionic polymerization method and a polymer hydrogenation technique thereof.
Examples of these thermoplastic elastomers include Dow ethylene octene rubber (EG series) and Exxon Vistamax series. In addition, since various products are commercially available from many companies, products having desired physical properties can be obtained and used.

(4) Compounding ratio The compounding amount of the component (d) used in the present invention is 1 to 30 parts by weight, preferably 5 to 23 parts by weight with respect to 100 parts by weight of the total amount of (a) and (b). Parts, more preferably 10 to 18 parts by weight. If the blending amount of the component (d) is less than 1 part by weight, sufficient impact strength may not be obtained in the fiber reinforced composition and molded product of the present invention, and if it exceeds 30 parts by weight, the fiber reinforced composition of the present invention may not be obtained. In addition, the rigidity of the molded body may be reduced.

5. Ingredient (e): Fatty acid amide (e)
Component (e) used in the present invention has the requirements defined in the following (Oi), and in the fiber reinforced composition and molded body of the present invention, the handling during molding becomes good. The fiber reinforced composition using the component (e) is particularly useful in applications for ribbed molded articles.
(Oi): a fatty acid amide represented by the following formula (A).
RCONH Formula ₂ (A)
[In Formula (1), R represents a C10-25 linear aliphatic hydrocarbon group. ]

(1) Requirements (Oi)
The component (e) used in the present invention is a fatty acid amide represented by the following formula (A).
RCONH Formula ₂ (A)
[In formula (A), R represents a C10-25 linear aliphatic hydrocarbon group. ]
Specifically, for example, amides of saturated fatty acids such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, linoleic acid amide, linolenic acid amide, erucic acid amide, arachidone Examples include amides of unsaturated fatty acids such as acid amides, eicosapentaenoic acid amides, and docosahexaenoic acid amides.
Among these, unsaturated fatty acid amides are preferable, and monounsaturated fatty acid amides such as erucic acid amide and oleic acid amide are more preferable.
In addition, you may use 2 or more types of component (e) together.

(2) Blending ratio The blending amount of the component (e) used in the present invention is 0.01 to 3 parts by weight, preferably 0.1 to 0.1 parts by weight with respect to 100 parts by weight of the total amount of (a) and (b). It is 02-2 weight part, More preferably, it is 0.05-1 weight part, Especially preferably, it is 0.1-0.5 weight part. If the blending amount of component (e) is less than 0.01% by weight, the effect of improving handling during molding may not be sufficiently obtained. If it exceeds 3 parts by weight, the fiber-reinforced composition of the present invention and There is a possibility that the rigidity and economy of the molded body may be lowered.

6). Optional addition component In the present invention, in addition to the component (a) to the component (e), if necessary, the effect of the present invention is further improved, for example, within the range not significantly impairing the effect of the present invention, or other effects. For example, a usual optional additive component can be added.
Specifically, molecular weight depressants such as peroxides, colorants such as pigments, antioxidants such as phenols, phosphorus and sulfur, light stabilizers such as hindered amines, and ultraviolet absorbers such as benzotriazoles Sorbents such as sorbitol, antistatic agents such as nonionics, dispersants such as organometallic salts, metal deactivators such as nitrogen compounds, flame retardants such as halogen compounds, antibacterials such as thiazoles Antifungal agents, plasticizers, neutralizers, polyolefin resins other than the component (a), component (e) and component (c), thermoplastic resins such as polyamide resins and polyester resins, other than the component (a) Examples include fillers such as talc, elastomers (rubber components) other than the component (d), lubricants other than the component (e), and the like.
These optional additional components may be used in combination of two or more, may be added to the composition, or may be added in advance to each of the components (A) to (O), respectively. Two or more of these components may be used in combination. In the present invention, the amount of the optional additive component is not particularly limited, but is usually about 0.01 to 0.8 part by weight with respect to 100 parts by weight of the total amount of the component (a) and the component (a). Yes, depending on the purpose.

(1) Type In addition to the effects of the present invention, the molecular weight lowering agent is effective for further imparting moldability (fluidity) and the like.
As the molecular weight depressant, for example, various organic peroxides, what are called decomposition (oxidation) accelerators, and the like can be used, and organic peroxides are preferable.
Specific examples of the organic peroxide include benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-methyl-2,5-di- ( Benzoylperoxy) hexane, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexyne-3, t-butyl-di-peradipate, t-butylperoxy-3,5,5- Trimethylhexanoate, methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-di-methyl-2,5-di- (t-butylperoxy) ) Hexane, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexyne-3,1,3-bis- ( -Butylperoxyisopropyl) benzene, t-butylcumyl peroxide, 1,1-bis- (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis- (t-butylper Oxy) cyclohexane, 2,2-bis-t-butylperoxybutane, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide , 1,1,3,3-tetra-methylbutyl hydroperoxide and 2,5-di-methyl-2,5-di- (hydroperoxy) hexane selected from the group consisting of one or more Things can be mentioned.

As a colorant, for example, an inorganic or organic pigment, in addition to the effects of the present invention, in addition to the effects of the present invention, the colored appearance, scratch resistance, appearance, texture, commercial value, It is effective for further imparting weather resistance and durability.
Specific examples of inorganic pigments include carbon blacks such as furnace carbon and ketjen carbon; titanium oxide; iron oxide (such as Bengala); chromic acid (such as yellow lead); molybdic acid; selenide sulfide; ferrocyanide Examples of organic pigments include poorly soluble azo lakes; soluble azo lakes; insoluble azo chelates; condensable azo chelates; other azo chelates such as azo chelates; phthalocyanine blue; phthalocyanine pigments such as phthalocyanine green; anthraquinones; Examples include selenium pigments such as thioindigo; dye lakes; quinacridone systems; dioxazine systems; and isoindolinone systems. Moreover, in order to make a metallic tone or a pearl tone, an aluminum flake; a pearl pigment can be contained. Moreover, dye can also be contained.

As a light stabilizer or ultraviolet absorber, for example, hindered amine compounds, benzotriazoles, benzophenones, salicylates, etc., in the fiber reinforced composition and molded article of the present invention, in addition to the effects of the present invention, weather resistance and durability It is effective for further grants.
Specific examples of the hindered amine compound include a condensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine; poly [[6- (1, 1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2 , 2,6,6-tetramethyl-4-piperidyl) imino]]; tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate; tetrakis ( 1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate; bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebake Bis-2,2,6,6-tetramethyl-4-piperidyl sebacate and the like, and examples of the benzotriazole type include 2- (2′-hydroxy-3 ′, 5′-di-t-butyl) Phenyl) -5-chlorobenzotriazole; 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, and the like. As the benzophenone series, 2-hydroxy- 4-methoxybenzophenone; 2-hydroxy-4-n-octoxybenzophenone and the like. Examples of salicylates include 4-t-butylphenyl salicylate; 2,4-di-t-butylphenyl 3 ′, 5′- Examples include di-t-butyl-4′-hydroxybenzoate.
Here, the method in which the light stabilizer and the ultraviolet absorber are used in combination is preferable because the effect of improving weather resistance, durability and the like is large.

As an antioxidant, for example, phenolic, phosphorus and sulfur antioxidants, in addition to the effects of the present invention, in the fiber reinforced composition and molded article of the present invention, heat stability, processing stability, It is effective for further imparting heat aging resistance.
As the antistatic agent, for example, an antistatic agent such as nonionic or cationic is effective for further imparting antistatic properties to the fiber-reinforced composition and molded body of the present invention in addition to the effects of the present invention. is there.
As these optional components, various products are commercially available from many companies, and desired products can be obtained and used according to the purpose.

7). Manufacturing method of fiber-reinforced polypropylene-based resin composition for molded body with ribs The resin fiber-reinforced composition of the present invention adds component (A) and component (I), or component (A) and component (I), Furthermore, as a component that is preferably used, at least one selected from the group consisting of component (c), component (d) and component (e) is further added as needed, and optionally added components, in the range of the content, It can manufacture by passing through the kneading | mixing process mix | blended by a conventionally well-known method, and melt-kneading.
Mixing is usually performed using a mixing device such as a tumbler, V blender, or ribbon blender, and melt kneading is usually performed by a single screw extruder, twin screw extruder, Banbury mixer, roll mixer, Brabender plastograph, kneader, stirring. Using a kneading machine such as a granulator (semi) melt kneading and granulating. When manufacturing by (semi) melt kneading and granulating, the blend of the above components may be kneaded at the same time, and each component may be divided and kneaded to improve performance. A method of kneading a part or all of the component (a) and a part of the component (a) and then kneading and granulating the remaining components can also be employed.

In the fiber reinforced composition of the present invention, the average length of the component (a) present in the fiber reinforced composition pellet obtained through the kneading step of melt kneading or in the molded body is 0.3 mm or more, preferably 0.8. It is preferable to manufacture by a composite method such that it is 4 mm or more and 2.5 mm or less.
In the present specification, the average length of the component (A) present in the fiber reinforced composition pellets or the molded product means a value obtained by calculating an average using a value measured by a digital microscope. For example, when the component (I) is glass fiber, the resin composition pellet or molded body of the present invention is burned, the ashed glass fiber is mixed with the surfactant-containing water, and the mixed water After dropping and diffusing the liquid on a thin glass plate, a length of 100 or more glass fibers is measured using a digital microscope (for example, VHX-900 type manufactured by Keyence Corporation), and the average value is calculated.

Moreover, as a preferable production method of the fiber reinforced composition of the present invention, for example, in melt kneading with a twin screw extruder, for example, after sufficiently melting and kneading component (a), component (c) and component (d), the component (B) may be fed by a side feed method or the like, and the bundled fibers may be dispersed while minimizing fiber breakage.
Also, for example, the so-called agitation granulation method in which components (a) to (e) are kneaded at a high speed in a Henschel mixer so that they are in a semi-molten state while mixing them (i) is minimized. Since it is easy to disperse | distribute a fiber, keeping it in a limit, it is one of the preferable manufacturing methods.
Furthermore, the component (a), the component (c) and the component (d) excluding the component (a) are melt-kneaded with an extruder or the like to form pellets, and the pellets and glass fiber-containing pellets or carbon fibers are contained. The production method of the fiber-reinforced composition of the present invention by mixing so-called “component (I) -containing pellets” such as pellets, and the method using the so-called “component (I) -containing masterbatch” are also the same reasons as described above. It is one of the preferable manufacturing methods.
As described above, a preferred method for producing the fiber-reinforced composition of the present invention includes a method of adding the component (a) after kneading the components other than the component (a) in the kneading step. The fiber reinforced composition of the present invention can be produced by the method.

8). Molding Method and Use of Molded Body The molding method for obtaining the molded body of the present invention can be performed without any particular limitation as long as it is a method for producing a ribbed molded body. That is, the fiber reinforced composition manufactured by the above method is, for example, injection molded (including gas injection molding, two-color injection molding, core back injection molding, sandwich injection molding), injection compression molding (press injection), and extrusion molding. It can be obtained by molding by a molding method capable of producing a ribbed molded body by a known molding method such as sheet molding and hollow molding. Among these, it can be said that injection molding or injection compression molding is a molding method capable of obtaining the molded body with ribs of the present invention, in which the effects of the fiber reinforced composition of the present invention are better exhibited.

The major features of the ribbed molded article of the present invention are that the weld appearance and the rib sink appearance are good, and that it has high rigidity and high impact strength.
Therefore, automotive interior and exterior such as instrument panels, glove boxes, console boxes, door trims, armrests, grip knobs, various trims, ceiling parts, housings, pillars, mudguards, bumpers, fenders, back doors, fan shrouds, etc. It can be suitably used for applications such as engine room parts, electrical and electronic equipment parts such as TVs and vacuum cleaners, various industrial parts, housing equipment parts such as toilet seats, and building material parts. In particular, by having the above-described characteristics, it is suitable for automobile parts.

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The evaluation methods, analysis methods and materials used in the examples are as follows.

1. Evaluation method, analysis method (1) Rigidity (flexural modulus):
Based on JIS K7171, it measured at the test temperature = 23 degreeC. As the test piece, the following flat test piece for evaluating physical properties was used. The unit is MPa.
-Molding machine = EC20 type injection molding machine manufactured by Toshiba Machine.
-Mold = two flat specimens for physical property evaluation (10 x 80 x 4t (mm)).
Molding conditions: molding temperature 220 ° C., mold temperature 30 ° C., injection pressure 50 MPa, injection time 5 seconds, cooling time 20 seconds.
In addition, about the bending elastic modulus, it determined as follows.
◎: 3000 MPa or more ○: 2000 MPa or more, less than 3000 MPa Δ: 1000 MPa or more, less than 2000 MPa x: less than 1000 MPa

(2) Impact strength (Charpy impact strength (notched)):
Based on JIS K7111, it measured at the test temperature = 23 degreeC. As the test piece, the above-mentioned flat test piece for evaluating physical properties was used. The unit is kJ / m ² .
The Charpy impact strength was determined as follows.
A: Not broken (NB)
○: 20 kJ / ^{m 2} or more △: 10 kJ / ^{m 2} or more, 20 kJ / ^{m 2} less ×: 10 kJ / ^m less than ²

(3) Weld appearance (opposed weld):
Test piece = flat plate shape (350 × 100 × 3 t (mm)).
・ Wrinkle surface = car interior leather wrinkle No. 421. Depth = 100 μm.
-Molding machine = IS220 injection molding machine manufactured by Toshiba Machine.
Molding condition = 2-point gate, molding temperature 200 ° C., mold temperature 30 ° C., injection pressure 50 MPa, filling time 4.5 s.
The test piece prepared on the said conditions was judged visually, and the conspicuousness of the weld was judged on the following reference | standard.
◎: Weld is not recognized at all ○: Weld is slightly recognized but not noticeable △: Weld is recognized but there is no problem in practical use

(4) Rib sink appearance:
Test piece = disc shape with ribs (φ100 × 4t (mm)).
-Molding machine = IS220 injection molding machine manufactured by Toshiba Machine.
Molding condition = 1 point gate, molding temperature 200 ° C., mold temperature 30 ° C., injection pressure 50 MPa, filling time 3.0 s.
The test piece created under the above conditions is visually determined, and the conspicuousness of rib sinks is determined according to the following criteria.
A: Rib sink is not recognized at all. O: Rib sink is slightly recognized but not noticeable.
(Triangle | delta): Although rib sink is recognized, it is satisfactory practically.
X: Rib sink is recognized and not suitable for practical use

(5) Comprehensive evaluation Comprehensive evaluation was performed as follows based on the determination results of the four items of flexural modulus, Charpy impact strength, weld appearance, and rib sink appearance.
○: There is no evaluation of x for 4 items, and it is suitable for practical use. X: There is one or more evaluations of x for 4 items, and it is not suitable for practical use.

(6) Component (A) and component (A-B) in component (A):
(A) TREF measuring method In the present Example, the TREF was specifically measured as follows. A sample was dissolved in orthodichlorobenzene (ODCB (containing 0.5 mg / mL BHT)) at 140 ° C. to prepare a solution. This was introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, subsequently cooled to −15 ° C. at a rate of 4 ° C./min, and held for 60 minutes. Thereafter, ODCB (containing 0.5 mg / mL BHT) as a solvent is flowed through the column at a flow rate of 1 mL / min, and the components dissolved in ODCB at −15 ° C. are eluted in the TREF column for 10 minutes, and then the temperature is raised. The column was linearly heated to 140 ° C. at a rate of 100 ° C./hour to obtain an elution curve.
The outline of the apparatus is as follows.
TREF column: 4.3 mmφ × 150 mm stainless steel column Column filler: 100 μm Surface inactive glass beads Heating method: Aluminum heat block Cooling method: Peltier element (Peltier element is cooled by water)
Temperature distribution: ± 0.5 ° C
Temperature controller: Chino Corporation Digital Program Controller KP1000 (Valve Oven)
Heating method: Air bath oven Measurement temperature: 140 ° C
Temperature distribution: ± 1 ° C
Valve: 6-way valve 4-way valve Injection method: Loop injection method Detector: Fixed wavelength infrared detector MIRAN 1A manufactured by FOXBORO
Detection wavelength: 3.42 μm
High-temperature flow cell: Micro flow cell for LC-IR Optical path length 1.5 mm Window shape 2φ × 4 mm long round Synthetic sapphire window Sample concentration: 5 mg / mL
Sample injection volume: 0.1 mL

(B) Determination of ethylene content in component (A-A) and component (A-B) (i) Separation of component (A-A) and component (A-B):
Based on the T (C) determined by the previous TREF measurement, a soluble component (A-B) in T (C) and an insoluble component in T (C) by a temperature rising column fractionation method using a preparative fractionator (A-A) and the ethylene content of each component was determined by NMR.
As the temperature rising column fractionation method, a detailed measurement method is shown in the following document, for example.
Macromolecules; 21, 314-319 (1988).
Specifically, the following method is used in the present invention.

(Ii) Sorting conditions:
A glass bead carrier (80-100 mesh) was packed in a cylindrical column having a diameter of 50 mm and a height of 500 mm, and maintained at 140 ° C.
Next, 200 mL of a sample ODCB solution (10 mg / mL) dissolved at 140 ° C. was introduced into the column. Thereafter, the temperature of the column was cooled to 0 ° C. at a rate of temperature decrease of 10 ° C./hour. After holding at 0 ° C. for 1 hour, the column temperature was heated to T (C) at a heating rate of 10 ° C./hour and held for 1 hour. In addition, the temperature control accuracy of the column through a series of operations was ± 1 ° C.
Next, while maintaining the column temperature at T (C), 800 mL of ODCB of T (C) is flowed at a flow rate of 20 mL / min to elute and recover components soluble in T (C) existing in the column. did.
Next, the column temperature is raised to 140 ° C. at a rate of temperature increase of 10 ° C./min, held at 140 ° C. for 1 hour, and then 800 mL of a solvent (ODCB) at 140 ° C. is flowed at a flow rate of 20 mL / min to obtain T ( Insoluble components were eluted and recovered in C).
The polymer-containing solution obtained by fractionation was concentrated to 20 mL using an evaporator, and then 5 times the amount of methanol was added to precipitate the polymer. The precipitated polymer was collected by filtration and dried overnight in a vacuum dryer.

(Iii) Determination of ethylene content by ¹³ C-NMR:
The ethylene content of each of the component (A-A) and the component (A-B) obtained by the fractionation is determined by analyzing a ¹³ C-NMR spectrum measured according to the following conditions by the proton complete decoupling method. It was.
Model: GSX-400 (carbon nuclear resonance frequency 400 MHz) manufactured by JEOL Ltd.
Solvent: ODCB / heavy benzene = 4/1 (volume ratio)
Concentration: 100 mg / mL
Temperature: 130 ° C
Pulse angle: 90 °
Pulse interval: 15 seconds Integration number: 5,000 times or more The spectrum was assigned according to the following document.
Macromolecules; 17, 1950 (1984).
The attribution of spectra measured under the above conditions is as shown in the table below. In the table, symbols such as Sαα follow the notation in the following literature, P represents methyl carbon, S represents methylene carbon, and T represents methine carbon.
Carman, Macromolecules; 10,536 (1977)

Hereinafter, when “P” is a propylene unit in a copolymer chain and “E” is an ethylene unit, six types of triads of PPP, PPE, EPE, PEP, PEE, and EEE may exist in the chain. As described in Macromolecules, 15 1150 (1982), the concentration of these triads and the peak intensity of the spectrum are linked by the following relational expressions <1> to <6>.
[PPP] = k × I (Tββ) <1>
[PPE] = k × I (Tβδ) <2>
[EPE] = k × I (Tδδ) <3>
[PEP] = k × I (Sββ) <4>
[PEE] = k × I (Sβδ) <5>
[EEE] = k × [I (Sδδ) / 2 + I (Sγδ) / 4} <6>
Here, [] indicates the fraction of triads, for example, [PPP] is the fraction of PPP triads in all triads.
Therefore, [PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1 <7>.
Further, k is a constant, I indicates the spectral intensity, and for example, I (Tββ) means the intensity of the 28.7 ppm peak attributed to Tββ.

By using the relational expressions <1> to <7> above, the fraction of each triad was determined, and the ethylene content was determined according to the following formula.
Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) × 100
The propylene random copolymer according to the present invention contains a small amount of a propylene hetero bond (2,1-bond and / or 1,3-bond), thereby producing the following minute peak.

In order to obtain an accurate ethylene content, it is necessary to include these peaks derived from heterogeneous bonds in the calculation, but it is difficult to completely separate and identify the peaks derived from heterogeneous bonds. Since the ethylene content in this example is small, the relational expression of <1> to <7> is the same as the analysis of the copolymer produced with the Ziegler-Natta catalyst that does not substantially contain a heterogeneous bond. It was decided to use it.
Conversion from mol% to wt% of ethylene content was performed using the following formula.
Ethylene content (% by weight) = (28 × X / 100) / {28 × X / 100 + 42 × (1−X / 100)} × 100
Here, X is the ethylene content in mol%. In addition, the ethylene content [E] W of the entire propylene-ethylene block copolymer is the ethylene content [E] A and [E] B of each of the component (A-A) and the component (A-B) measured from the above. And the weight ratio W (A) and W (B) weight% of each component calculated from TREF, and the following formula was used.
[E] W = {[E] A × W (A) + [E] B × W (B)} / 100 (% by weight)

(7) Melting peak temperature (Tm) of component (a):
Using a Seiko Instruments DSC6200 model, take 5.0 mg of sample, hold it at 200 ° C for 5 minutes, crystallize it to 40 ° C at a rate of 10 ° C / min. Measured after melting.

(8) Peak of tan δ curve of component (a):
It was measured by solid viscoelasticity measurement. The sample used was cut into a strip shape of 10 mm width × 18 mm length × 2 mm thickness from a 2 mm thick sheet formed by injection molding under the following conditions.
The apparatus used was ARES manufactured by Rheometric Scientific.
Standard number: JIS-7152 (ISO294-1)
Frequency: 1Hz
Measurement temperature: From -60 ° C. until the sample melts.
Strain: in the range of 0.1-0.5% Molding machine: TU-15 injection molding machine manufactured by Toyo Machine Metal Co., Ltd. Molding machine set temperature: 80, 80, 160, 200, 200, 200 ° C. from below the hopper
Mold temperature: 40 ℃
Injection speed: 200 mm / sec (speed in the mold cavity)
Injection pressure: 800 kgf / cm ²
Holding pressure: 800 kgf / cm ²
Holding time: 40 seconds
Mold shape: Flat plate (2mm thickness, 30mm width, 90mm length)

(9) Melt flow rate (MFR)
Measured in accordance with JIS K7210: 1999, Method A, Condition M (230 ° C., 2.16 kg load). The unit is g / 10 minutes.

2. Material (1) Component (A): Propylene-ethylene block copolymer (A)
(All of these are commercially available pellets to which an antioxidant and a neutralizing agent have been added.)
A-1: The following grades of composition and physical properties of polypropylene (Wellnex series) manufactured by Nippon Polypro Co., Ltd. were used.
This material is polymerized with a metallocene catalyst, 56.0% by weight of propylene-ethylene random copolymer component (A-A1) having an ethylene content of 1.8% by weight in the first step, and component (A) in the second step. Obtained by sequential polymerization of 44.0% by weight of propylene-ethylene random copolymer component (A-B1) containing 9.2% by weight of ethylene more than -A1), measured by DSC method In the temperature-loss tangent curve obtained by solid viscoelasticity measurement, the tan δ curve has a single peak at −8 ° C. and the copolymer (A- 1) The total MFR (230 ° C., 2.16 kg load) is 6 g / 10 min.
A-2: The following grade of composition and physical properties of polypropylene (Wellnex series) manufactured by Nippon Polypro Co., Ltd. was used.
This material is polymerized with a metallocene catalyst, 56.2% by weight of a propylene-ethylene random copolymer component (A-A2) having an ethylene content of 2.0% by weight in the first step, and a component (a) in the second step. Obtained by sequential polymerization of 43.8% by weight of propylene-ethylene random copolymer component (A-B2) containing 9.2% by weight of ethylene more than -A2), measured by DSC method In the temperature-loss tangent curve obtained by solid viscoelasticity measurement, the tan δ curve has a single peak at −8 ° C., and the copolymer (A- 2) The total MFR (230 ° C., 2.16 kg load) is 18 g / 10 min.
A-3: Grades of the following composition and physical properties of polypropylene (Wintech series) manufactured by Nippon Polypro Co., Ltd. were used.
The material was polymerized with a metallocene catalyst, and after the first step, a propylene-ethylene random copolymer component (A-A3) having an ethylene content of 3.4% by weight was obtained, and then the second step was not performed. In the temperature-loss tangent curve obtained by solid viscoelasticity measurement, the melting peak temperature (Tm) measured by DSC method is 133 ° C., and the tan δ curve has a single peak at 1 ° C. (A-3) The total MFR (230 ° C., 2.16 kg load) is 25 g / 10 min.
A-4: The grade of the following composition and physical properties of polypropylene (Novatec series) manufactured by Nippon Polypro Co., Ltd. was used.
The material is polymerized with a Ziegler catalyst, ethylene is not used in the first step, the propylene homopolymer component (A-A4) is 73.0% by weight, and the second step is more than the component (A-A4). The melting peak temperature measured by DSC method, obtained by sequential polymerization of 27.0% by weight of a propylene-ethylene random copolymer component (A-B4) containing 37.0% by weight of a large amount of ethylene (Tm) is 161 ° C. In the temperature-loss tangent curve obtained by solid viscoelasticity measurement, the tan δ curve has peaks at −40 ° C. and −1 ° C., and the MFR ( 230 ° C., 2.16 kg load) is 28 g / 10 min.
A-5: The following grade of composition and physical properties of polypropylene (Novatec series) manufactured by Nippon Polypro Co., Ltd. was used.
The material is polymerized with a Ziegler catalyst, ethylene is not used in the first step, the propylene homopolymer component (A-A5) is 92.0% by weight, and the second step is more than the component (A-A5). Melting peak temperature measured by DSC method, obtained by sequential polymerization of 8.0% by weight of propylene-ethylene random copolymer component (A-B5) containing 60.0% by weight of a large amount of ethylene In the temperature-loss tangent curve obtained by solid viscoelasticity measurement at (Tm) of 161 ° C., the tan δ curve has peaks at −40 ° C. and −1 ° C., and the MFR of the entire copolymer (A-5) ( 230 ° C., 2.16 kg load) is 60 g / 10 min.

(2) Component (I): Fiber (I)
A-1: Glass fiber T480H manufactured by Nippon Electric Glass Co., Ltd. (chopped strand, fiber diameter 10 μm, length 4 mm).
(3) Component (C): Modified polyolefin (C)
C-1: Maleic anhydride-modified polypropylene manufactured by Mitsubishi Chemical Corporation (product number: CMPP2) with an acid modification amount (graft ratio) = 0.7 wt%.
(4) Component (D): Thermoplastic elastomer (D)
D-1: Engage EG8200 (manufactured by Dow Chemical Company, ethylene-octene copolymer elastomer, MFR (230 ° C., 2.16 kg load) 10 g / 10 min, density 0.870 g / cm ^3, shape = pellet).
(5) Component (e): Fatty acid amide (e)
O-1: Erucic acid amide (Neutron-S) manufactured by Nippon Seika Co., Ltd.
(6) Optional component (f): Peroxide (f)
K-1: Perbutyl P-40 manufactured by NOF Corporation (molecular weight-decreasing agent obtained by diluting 1,3-di- (t-butylperoxyisopropyl) benzene to 40%).

3. Examples and Comparative Examples [Examples 1-2 and Comparative Examples 1-5]
(1) Manufacture of fiber-reinforced polypropylene resin composition for ribbed molded article The above components (A) to (F) are blended in the proportions shown in Table 4 together with the following additives, and kneaded under the following conditions: Granulated to produce pellets.
At this time, 0.1 parts by weight of IRGANOX 1010 manufactured by BASF and 0.05 parts by weight of IRGAFOS 168 manufactured by BASF were blended per 100 parts by weight of the total composition comprising the components (a) to (f).
Kneading apparatus: “KZW-15-MG” type twin screw extruder manufactured by Technobel.
Kneading conditions: temperature = 200 ° C., screw rotation speed = 400 rpm, discharge amount = 3 kg / Hr.

(2) Molding of ribbed molded body Using the obtained fiber-reinforced polypropylene resin composition pellets for ribbed molded bodies, injection molding was performed under the above-described conditions, and the fiber-reinforced polypropylene resin composition for ribbed molded bodies was molded. Various test pieces were used.

(3) Evaluation Performance evaluation was performed on the above molded product. The results are shown in Table 5.

4). Evaluation From the results shown in Tables 3 to 5, Examples 1 and 2 satisfying the invention requirements of the fiber-reinforced composition for a ribbed molded article of the present invention and the molded article have both good weld appearance and rib sink appearance. In addition, it has high rigidity and high impact strength.
As described above, since it is determined to be good in all evaluations, the fiber reinforced composition for a molded article with a rib according to the present invention includes an instrument panel, a glove box, a console box, a door trim, an armrest, a grip knob, and various trims. Parts, ceiling parts, housings, pillars, mudguards, bumpers, fenders, back doors, fan shrouds, and other automotive interior and engine room parts, electrical and electronic equipment parts such as TVs and vacuum cleaners, and various industrial parts It has become clear that it can be suitably used for applications such as housing equipment parts such as toilet seats and building material parts.

  On the other hand, in the comparative example which does not satisfy the specific matter of the present invention, the polypropylene resin composition having the composition shown in Comparative Examples 1 to 5 and its molded product have a poor performance balance, and at least any one of them. It is determined that the evaluation items cannot be used practically, which is inferior to those of Examples 1 and 2.

The fiber-reinforced polypropylene resin composition for a molded article with ribs of the present invention and a molded article obtained by molding the composition have good weld appearance and rib sink appearance, and have both high rigidity and high impact strength.
Therefore, automotive interior and exterior such as instrument panels, glove boxes, console boxes, door trims, armrests, grip knobs, various trims, ceiling parts, housings, pillars, mudguards, bumpers, fenders, back doors, fan shrouds, etc. It can be suitably used for applications such as engine room parts, electrical and electronic equipment parts such as TVs and vacuum cleaners, various industrial parts, housing equipment parts such as toilet seats, and building material parts.

Claims (6)

The following propylene-ethylene block copolymer (a) 40% to 99% by weight and fiber (a) 1% to 60% by weight (however, the total amount of (a) and (a) is 100% by weight) And a fiber-reinforced polypropylene resin composition for a molded article with ribs.
Propylene-ethylene block copolymer (a): having the requirements defined in the following (a-i) to (a-iv).
(A-i): Using a metallocene-based catalyst, 30% to 95% by weight of propylene alone or a propylene-ethylene random copolymer component (A-A) having an ethylene content of 7% by weight or less in the first step; By sequentially polymerizing 70 wt% to 5 wt% of a propylene-ethylene random copolymer component (A-B) containing 3 to 20 wt% more ethylene than the component (A-A) in two steps. (However, the total amount of (A-A) and (A-B) is 100% by weight).
(A-ii): Melting peak temperature (Tm) measured by DSC method is 110 ° C to 150 ° C.
(A-iii): In the temperature-loss tangent curve obtained by solid viscoelasticity measurement, the tan δ curve has a single peak at 0 ° C. or lower.
(A-IV): The melt flow rate (MFR: 230 ° C., 2.16 kg load) of the entire propylene-ethylene block copolymer (A) is 0.5 g / 10 min to 200 g / 10 min.
Fiber (A): It has the requirements specified in (I-i) below.
(Ii): At least one selected from the group consisting of glass fiber, carbon fiber and whisker.   2. The fiber-reinforced polypropylene resin composition for a molded article with ribs according to claim 1, wherein the fibers (a) are glass fibers.   The fiber-reinforced polypropylene resin composition for a molded article with ribs according to claim 2, wherein the glass fiber has a length of 2 mm or more and 20 mm or less. Furthermore, the following modified polyolefin (c) 0.01 to 10 parts by weight, thermoplastic elastomer (d) 1 to 30 parts by weight, and fatty acid amide with respect to 100 parts by weight of the total amount of (a) and (b) (E) The fiber-reinforced polypropylene resin composition for a molded article with ribs according to any one of claims 1 to 3, which contains at least one selected from the group consisting of 0.01 to 3 parts by weight.
Modified polyolefin (c): It has the requirements specified in the following (ui).
(Ui): At least one selected from the group consisting of acid-modified polyolefin and hydroxy-modified polyolefin.
Thermoplastic elastomer (D): It has the requirements specified in the following (E-i) and (E-ii).
(D -i): a density of ^{0.86g / cm 3 ~0.92g / cm 3} .
(D-ii): Melt flow rate (230 ° C., 2.16 kg load) is 0.5 g / 10 min to 100 g / 10 min.
Fatty acid amide (e): having the requirements specified in (i) below.
(Oi): a fatty acid amide represented by the following formula (A).
RCONH Formula ₂ (A)
[In formula (A), R represents a C10-25 linear aliphatic hydrocarbon group. ]   The molded object with a rib formed by shape | molding the fiber reinforced polypropylene resin composition for molded objects with a rib of any one of Claims 1 thru | or 4.   The molded body with ribs according to claim 5, which is an automobile part.

Images