JP5271792B2 - Polypropylene masterbatch containing fibrous filler, resin composition comprising the same, injection molding method and injection molded body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polypropylene-based master batch containing a fibrous filler having excellent molded appearance, physical properties (rigidity, impact strength) and fluidity (moldability), a high improvement effect of economical efficiency and excellent correspondence to various requirements such as dimensions and physical properties, and to provide a resin composition composed of the same, an injection molding method and an injection molded product. <P>SOLUTION: The polypropylene-based master batch containing the fibrous filler comprises a propylene-based resin (A), the fibrous filler (B) and a fatty acid metal salt (C). <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a polypropylene-based masterbatch, a resin composition comprising the same, an injection molding method, and an injection-molded body, and more specifically, excellent molding appearance, good physical property balance and fluidity, great economic improvement effect, dimensions The present invention relates to a fibrous filler-containing polypropylene master batch, a resin composition comprising the same, an injection molding method, and an injection-molded article (including an injection compression-molded article) that are excellent in compatibility with various required performances such as physical properties.

  Conventionally, polypropylene-based resins have good physical properties and moldability, and their use range is rapidly expanding as an environmentally friendly material. In particular, for automotive parts and the like, lightweight and excellent polypropylene resin products are provided. Among such products, resin compositions and injection molded articles using polypropylene master batches containing fibrous fillers are provided. is there.

  Polypropylene masterbatch containing various fillers is used mainly to improve the economics of polypropylene resin products, and is usually a resin composition blended with polypropylene resin pellets (hereinafter also referred to as dilution pellets) that do not contain fillers. As a direct injection molding or injection compression molding machine. As a manufacturing method of these master batches, a polypropylene resin and a filler are mixed in a mixer and supplied to a melt kneading extruder such as a twin screw extruder and melt kneaded, or a stirring granulator such as a Henschel mixer. There is known a method of supplying to a melt and kneading (see, for example, Patent Document 1).

Among various fillers, fibrous fillers, especially fibrous fillers (also called whiskers), which have a relatively large effect of improving the balance of physical properties such as rigidity, are relatively bulky, and because of their bulk, they are mixed and kneaded with polypropylene resins. Is difficult or is fine, it tends to form filler aggregates during mixing and kneading. For this reason, the masterbatch using the same often has an insufficient effect of improving the economy and the appearance of the molded product.
With regard to the improvement of mixing and kneading properties of fibrous fillers, particularly fibrous fillers having a small fiber diameter, a method of using those granular aggregates in the production of the filler-containing resin composition is disclosed (for example, Patent Documents). 2).
However, this method needs to be used in combination with fillers of other shapes, or the content concentration of the fibrous filler itself remains at a relatively low level, and there is a problem that it is difficult to improve economy from the viewpoint of application to a masterbatch. .

  In addition, as described above, polypropylene-based masterbatch containing fibrous fillers, particularly fibrous fillers with extremely small fiber diameters, are likely to form filler aggregates, and the aggregates are scattered in the molded product, resulting in poor appearance. As a method for improving this, a thermoplastic resin and a part of the filler (fibrous filler) are melted and kneaded in advance with an extruder to obtain pellets, and then the pellets and the other fillers A method for producing master batch pellets is disclosed in which the agglomerates are pelletized with an extruder after being agglomerated by high-speed stirring with a mixer having a stirring blade inside (see, for example, Patent Document 3). .) However, since this method requires extrusion kneading, stirring kneading, and further extrusion kneading, there are many manufacturing steps, and since many kneadings are required, the components (thermoplastic resin and fibrous filler) constituting the master batch are required. There are many thermal history times (before three times) that have a great influence on physical properties and appearance (total 3 times), and the number of breakage opportunities for fibrous fillers that are likely to deteriorate physical properties (rigidity, etc.) is the same (total) 3 times).

Further, the first propylene polymer (AI) and the fibrous inorganic filler (B) are set to a weight ratio ((AI) / (B)) of (AI) and (B) of 3 / 7-7 / 3, and melt-kneaded to obtain a resin composition (MB), and the resin composition (MB) obtained in the first step is further mixed with a second propylene polymer (A -II), a non-fibrous inorganic filler (C), an olefin-based elastomer and / or a vinyl aromatic compound-containing elastomer (D), and melt-kneaded to obtain a resin composition in a second step In the method for producing a resin composition, the resin composition (MB) is produced as a pellet in the first step, and the pellet is used in the second step. Similarly, in the first step, the propylene polymer (AI ) And 100 wt parts of the total weight of the fibrous inorganic filler (B) The resin composition (MB) was added using 0.3 to 3 parts by weight of the lubricant (F) and a kneader having a ratio (L / D) of the screw length (L) to the diameter (D) of 10 to 25. ) Has been disclosed (see, for example, Patent Document 4).
However, since this method also requires extrusion kneading twice, the above-described heat for the components (propylene polymer (AI) and fibrous inorganic filler (B) constituting the resin composition (MB) in the first step is used. The number of histories is large (2 times in total), and the number of fiber filler breakage opportunities is the same (2 times in total).

JP 59-220319 A JP-A-8-41257 JP 2000-127152 A JP 2006-83369 A

  Under such circumstances, the problems of the conventional polypropylene masterbatch containing a fibrous filler, the resin composition comprising the same, and the injection molded article are solved, and injection molded articles for various molded articles, particularly for interior and exterior automobile parts are obtained. It is suitable for processing, has excellent molding appearance, has a great influence on physical properties and appearance, reduces the number of heat history during processing and the number of breakage opportunities of fibrous filler, has a good balance of physical properties, has a large economic improvement effect, dimensions There is a need for research and development on a polypropylene-based masterbatch containing a fibrous filler, a resin composition comprising the same, an injection molding method, and an injection-molded article that are excellent in compatibility with various required performances such as physical properties and physical properties.

The object of the present invention is to suppress the occurrence of bright spots and flow marks in spite of containing fibrous fillers when used in injection molded articles for interior and exterior automotive parts, etc. Excellent molding appearance, greatly affecting physical properties and appearance (before molding) Reduces the number of heat history during processing and the chance of breakage of the fibrous filler, has a good balance of physical properties, and also improves economic efficiency Corresponding to various required performance such as dimensions and physical properties (by finely adjusting the compounding amount of the master batch, the shrinkage rate of the resin composition containing it can be increased or decreased to adjust the dimensions of the molded body The masterbatch has a large compounding amount effect, such as the ability to fine-tune the physical properties such as rigidity, and the like. There to be provided.
Incidentally, the bright spot means point-like foreign matters mainly due to filler aggregates and the like, and the flow mark means a tiger-striped pattern associated with the resin flow.

  As a result of intensive studies to solve the above problems, the present inventors blended a propylene-based resin (component A), a fibrous filler (component B), and a fatty acid metal salt (component C) to obtain a fibrous form. When a filler-containing polypropylene masterbatch is mixed or / and kneaded with a polypropylene resin (diluted pellet) to form a resin composition, the dispersion is good even though there is little opportunity to knead and disperse the fibrous filler. For example, it suppresses the generation of bright spots and flow marks and has excellent molding appearance, which greatly affects the physical properties and appearance (before molding) and reduces the number of thermal history and the number of breakage opportunities for fibrous filler. As a result, the fiber has a good balance of physical properties, good fluidity, a large economic improvement effect, and excellent compatibility with various required performances such as dimensions and physical properties. Filler-containing polypropylene masterbatch, a resin composition comprising the same, an injection molding method and an injection molded article found that to obtain, based on these findings, the present invention has been completed.

That is, according to 1st invention of this invention, propylene resin (component A) 30 to 75 weight%, fibrous filler (component B) 25 to 70 weight%, and fatty acid metal salt (component C) component A And a fibrous filler-containing polypropylene masterbatch containing 0.01 to 10 parts by weight per 100 parts by weight of the total of component B ,
The propylene resin (component A) is at least partially composed of a linear propylene polymer portion and a linear ethylene / propylene random copolymer portion, and has the following characteristics (i) to (vii). A linear propylene / ethylene block copolymer, and
A fibrous filler-containing polypropylene master batch is provided, wherein the fibrous filler (component B) is fibrous basic magnesium sulfate having an average fiber diameter of 2 μm or less and an average fiber length of 100 μm or less .

Characteristic (i): The melt flow rate (230 ° C., 2.16 kg load) of the linear propylene polymer portion is 120 g / 10 min or more.
Characteristic (ii): The composition ratio of the linear ethylene / propylene random copolymer portion to the entire linear propylene / ethylene block copolymer (component A) is 2 to 50% by weight.
Characteristics (iii): The intrinsic viscosity _{[eta] copoly} of linear ethylene-propylene random copolymer portion is 5.3~12.0dl / g.
Characteristic (iv): The ethylene content of the linear ethylene / propylene random copolymer portion is 15 to 80% by weight based on the total amount of the linear ethylene / propylene random copolymer.
Characteristic (v): Melt flow rate (230 ° C., 2.16 kg load) is 50 g / 10 min or more.
Characteristic (vi): Ratio (Q value: Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn) is 7-13.
Characteristic (vii): Shows strain hardening in 180 ° C. extensional viscosity measurement.

According to the second invention of the present invention, in the first invention, the propylene-based resin (component A) comprises the linear propylene / ethylene block copolymer and the other propylene / ethylene block copolymer. A fibrous filler-containing polypropylene-based masterbatch comprising a coalescence is provided.

Moreover, according to the third invention of the present invention, in the first or second invention, further, talc is contained in an amount of 40 to 1000 parts by weight per 100 parts by weight of the fibrous filler (component B). A filler-containing polypropylene-based masterbatch is provided.

According to a fourth aspect of the present invention, the fibrous filler-containing polypropylene according to any one of the first to third aspects, wherein the fatty acid metal salt (component C) is a basic fatty acid metal salt. A system masterbatch is provided.

According to a fifth aspect of the present invention, the fibrous filler-containing polypropylene masterbatch according to any one of the first to fourth aspects and a polypropylene resin (component D) are mixed or kneaded. A resin composition is provided.

According to the sixth invention of the present invention, the fibrous filler-containing polypropylene masterbatch according to any one of the first to fourth inventions, a polypropylene resin (component D) and an elastomer (component E) or / and non- A resin composition characterized by mixing or kneading a fibrous filler (component F) is provided.

According to the seventh invention of the present invention, the fibrous filler-containing polypropylene masterbatch according to any one of the first to fourth inventions, a polypropylene resin (component D) and an elastomer (component E) or / and There is provided a resin composition characterized by mixing or kneading a resin composition mixed or kneaded with a non-fibrous filler (component F).

According to an eighth aspect of the present invention, there is provided the resin composition according to the fifth aspect , wherein the polypropylene resin (component D) is a propylene / ethylene block copolymer.

According to the ninth invention of the present invention, in the sixth or seventh invention, the polypropylene resin (component D) is a propylene / ethylene block copolymer, and the non-fibrous filler (component F) is talc. A resin composition is provided.

Further, according to the tenth aspect of the present invention, an injection molding method, which comprises molding a resin composition according to any one of aspects 5-9 it is provided.

The 11 th aspect of the present invention, injection molded article is provided, characterized in that the resin composition according to any one of aspects 5-9.

As described above, the present invention relates to a fibrous filler-containing polypropylene masterbatch and the like, and preferred embodiments include the following.
(1) In the first invention, the linear propylene polymer portion of the linear propylene / ethylene block copolymer is polymerized by a multistage polymerization method, preferably a two-stage polymerization method. A fibrous master-containing polypropylene masterbatch.
(2) In the first invention, the linear propylene / ethylene block copolymer has strain hardening in 180 ° C. extensional viscosity measurement, and in 180 ° C extensional viscosity measurement, the strain rate is 1.0 / sec. A fibrous filler-containing polypropylene masterbatch having a strain hardening degree (λmax) value of 2.0 or more.
(3) In the fourth invention, the metal in the basic fatty acid metal salt is at least one selected from magnesium, calcium or zinc, and is a fibrous filler-containing polypropylene masterbatch.
(4) In the seventh invention, a resin composition obtained by kneading a polypropylene resin (component D) and an elastomer (component E) or / and a non-fibrous filler (component F) in advance is a screw diameter used in an enlargement facility. A resin composition characterized by being melt-kneaded using a kneader of 250 mm or more.

The fibrous filler-containing polypropylene masterbatch of the present invention, a resin composition comprising the same, an injection molding method and an injection-molded article contain a fibrous filler when used in an injection-molded article for interior and exterior automobile parts, etc. Although there are few opportunities to knead and disperse the fibrous filler, the number of heat histories during processing and the number of chances of breakage of the fibrous filler are excellent because of its good dispersion, etc. (That is, the number of times until injection molding such as injection molding is only one), the balance of physical properties is good, the fluidity is good, the economic efficiency is greatly improved, and there are various dimensions and physical properties. Excellent compatibility with required performance.
For this purpose, applications such as trims, instrument panels, pillars, various housings, fenders, bumpers, trunk interiors, automobile interior and exterior parts, television and other home appliance parts, electronic product parts, various industrial parts, building material parts, etc. Can be suitably used.

The present invention comprises a propylene-based resin (component A, hereinafter simply referred to as component A) 30 to 75% by weight, a fibrous filler (component B, hereinafter also simply referred to as component B) 25 to 70% by weight, a fatty acid metal salt (Component C, hereinafter also simply referred to as Component C) A fibrous filler-containing polypropylene masterbatch containing 0.01 to 10 parts by weight of each component per 100 parts by weight of Component A and Component B in total , A resin composition comprising the same, an injection molding method, and an injection molded article.
Hereinafter, the fibrous filler-containing polypropylene master batch (hereinafter also simply referred to as MB), each component of the resin composition comprising the same, production, production of an injection-molded product (injection molding method), and the like will be described in detail.

[I] Constituent components of fibrous filler-containing polypropylene masterbatch (MB) Propylene resin (component A)
The propylene-based resin (component A) used in the MB of the present invention is a component constituting the base material of the MB of the present invention, and is excellent in the MB of the present invention, a resin composition comprising the same, and injection molding and injection molded articles. Furthermore, it has characteristics that contribute to maintaining and improving the molding appearance, physical property balance, moldability, productivity, and the like.

(1) Kind As the kind of component A, a propylene homopolymer, a copolymer of propylene and an α-olefin such as a propylene / ethylene random copolymer or a propylene / ethylene block copolymer, and a propylene / vinyl compound Copolymers, copolymers of propylene and vinyl esters, copolymers of propylene and unsaturated organic acids or derivatives thereof, copolymers of propylene and conjugated dienes, copolymers of propylene and nonconjugated polyenes And a mixture thereof.
Of these, a copolymer of propylene and ethylene is preferable, and a propylene / ethylene block copolymer is more preferable.

Here, in Component A, at least a part thereof is composed of a linear propylene polymer portion and a linear ethylene / propylene random copolymer portion, and has the following characteristics (i) to (vii). A linear propylene / ethylene block copolymer is particularly preferred.
The linear propylene / ethylene block copolymer has a feature that contributes to the development of a particularly excellent molding appearance and physical property balance in the MB of the present invention, the resin composition comprising the same, and injection molding and injection molding.
Characteristic (i): Melt flow rate (hereinafter referred to as MFR) (230 ° C., 2.16 kg load) of the linear propylene polymer portion is 120 g / 10 min or more.
Characteristic (ii): The composition ratio of the linear ethylene / propylene random copolymer portion to the entire linear propylene / ethylene block copolymer is 2 to 50% by weight.
Characteristics (iii): The intrinsic viscosity _{[eta] copoly} of linear ethylene-propylene random copolymer portion is 5.3~12.0dl / g.
Characteristic (iv): The ethylene content of the linear ethylene / propylene random copolymer portion is 15 to 80% by weight based on the total amount of the linear ethylene / propylene random copolymer.
Characteristic (v): MFR (230 ° C., 2.16 kg load) is 50 g / 10 min or more.
Characteristic (vi): Ratio (Q value: Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn) is 7-13.
Characteristic (vii): Shows strain hardening in 180 ° C. extensional viscosity measurement.

Here, the term “linear” in the linear propylene polymer portion, the linear ethylene / propylene random copolymer portion or the linear propylene / ethylene block copolymer is a branched structure other than the methyl branched structure. Is extremely small, and this is a structure often found in ordinary polypropylene resins.
For example, it can be confirmed by ¹³ C-NMR analysis that no peak is observed at 31.5 to 31.7 ppm based on branched carbon (see Macromol. Chem. Phys. 2003, Vol. 204, page 1738).

  Although the linear propylene / ethylene block copolymer has a linear structure as described above, it exhibits strain hardening. This strain hardening property is usually said to be caused by molecular entanglement. In order to develop the strain hardening property, for example, the molecular weight of the linear propylene polymer portion and the linear propylene / ethylene random copolymer weight are used. Examples of the method include increasing the difference in molecular weight of the combined portion, and increasing the compatibility between the linear propylene polymer portion and the linear propylene / ethylene random copolymer portion.

The linear propylene / ethylene block copolymer not only satisfies these requirements, but the dispersion structure of the linear ethylene / propylene random copolymer portion in the linear propylene polymer portion is unique, that is, In the case of a general propylene / ethylene block copolymer (in this case, when subjected to shearing, the ethylene / propylene random copolymer portion is rejected and aggregated at the interface of the propylene polymer portion and dispersed individually. )), A state similar to a network (that is, a linear ethylene / propylene random copolymer portion soaks into the linear propylene polymer portion in a network) is exhibited. Therefore, it is considered to show strain hardening.
In addition, by exhibiting a state that approximates a kind of network, the compatibility between the linear propylene polymer portion and the linear ethylene / propylene random copolymer portion is further enhanced, Has been considered.

  The effect of exhibiting strain hardening is that the dispersion of component B becomes more uniform due to the above-mentioned network-like dispersion structure in the MB of the present invention, the resin composition comprising the same, injection molding and injection molded body, and the like. It is easy to suppress the generation of bright spots and flow marks, and the molding appearance and balance of physical properties are easily improved.

(2) Characteristics of Component A Preferred component A is, as described above, a linear propylene / ethylene block copolymer comprising a linear propylene polymer portion and a linear ethylene / propylene random copolymer portion, or And a linear propylene / ethylene block copolymer comprising a linear propylene polymer portion and a linear ethylene / propylene random copolymer portion, and other propylene / ethylene block copolymers. The characteristics of each component will be described below.

(2-a) Component A other than linear propylene / ethylene block copolymer
The total MFR (230 ° C., 2.16 kg load) of component A other than the linear propylene / ethylene block copolymer used in the MB of the present invention needs to be 50 g / 10 min or more, preferably 60 g / 10. More than a minute. When the MFR is less than 50 g / 10 min, it is difficult to produce MB, or component B is easily broken, and the molded appearance and physical property balance are reduced in MB, a resin composition comprising the same, injection molding and injection molded body. To do.

(2-b) Linear propylene / ethylene block copolymer characteristics (i):
The MFR (230 ° C., 2.16 kg load) of the linear propylene polymer portion in the linear propylene / ethylene block copolymer used as necessary for the MB of the present invention is 120 g / 10 min or more, preferably 150 to 3000 g / 10 minutes, more preferably 250 to 2000 g / 10 minutes. When the MFR satisfies the above range, the appearance of molding and the balance of physical properties are further improved in MB, a resin composition comprising the same, injection molding, and injection molded body. The MFR is the MFR when the polymerization of the linear propylene polymer portion is completed, and when performing the multistage polymerization, the MFR is the MFR of the linear propylene polymer portion taken out from the final polymerization tank.

Characteristic (ii):
The composition ratio of the linear ethylene / propylene random copolymer portion in the linear propylene / ethylene block copolymer used as necessary for the MB of the present invention to the entire linear propylene / ethylene block copolymer is: It is 2 to 50% by weight, preferably 5 to 40% by weight, and more preferably 7 to 20% by weight.
That is, the constituent ratio of the linear propylene polymer portion to the entire linear propylene / ethylene block copolymer is 50 to 98% by weight, preferably 60 to 95% by weight, more preferably 80 to 93% by weight. . When the linear ethylene / propylene random copolymer portion satisfies the above range, the impact strength, molding appearance and rigidity can be improved to a better level in MB, a resin composition comprising the same, injection molding and injection molding. I can do it.

Characteristic (iii):
The intrinsic viscosity _{[eta] copoly} of MB linear ethylene-propylene random copolymer portion of the linear propylene-ethylene block copolymer to be used according to need of the present invention, 5.3~12.0dl / g, preferably 6.0 to 10.0 dl / g, more preferably 6.5 to 9.5 dl / g. In order to facilitate the expression of the molding appearance (bright spot, flow mark) and impact strength at a better level in the MB of the present invention, the resin composition comprising the same, injection molding and injection molded article, the intrinsic viscosity [η] _copolymer is It is preferable to be in the above range.

Characteristic (iv):
The ethylene content of the linear ethylene / propylene random copolymer portion in the linear propylene / ethylene block copolymer used as necessary for the MB of the present invention is the total content of the linear ethylene / propylene random copolymer. It is 15-80 weight% with respect to it, Preferably it is 20-70 weight%, More preferably, it is 25-45 weight%. In the MB of the present invention, the resin composition comprising the same, injection molding and injection-molded body, the ethylene content is preferably within the above-mentioned range in order to make the molding appearance and impact strength easily manifest at a better level.

Characteristic (v):
The MFR (230 ° C., 2.16 kg load) of the entire linear propylene / ethylene block copolymer used as necessary for the MB of the present invention needs to be 50 g / 10 min or more, preferably 80 g / 10. Min or more, more preferably 105 to 500 g / 10 min. When the MFR satisfies the above range, MB is easy to manufacture, and component B is difficult to break, and in MB, a resin composition comprising the same, injection molding and injection molded article, moldability, molding appearance and balance of physical properties Can be improved to a better level.

Characteristic (vi):
The ratio (Q value: Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) representing the molecular weight distribution of the entire linear propylene / ethylene block copolymer used as necessary for the MB of the present invention. Is 7-13, preferably 8-12. When the Q value satisfies the above range, a good molded appearance can be exhibited in MB, a resin composition comprising the same, injection molding and injection-molded body, and the block copolymer can be stably produced.

Characteristic (vii):
The linear propylene / ethylene block copolymer used as necessary for the MB of the present invention exhibits strain hardening in 180 ° C. extensional viscosity measurement. The effect of showing strain-hardening properties in this 180 ° C. elongational viscosity measurement is that the MB of the present invention and the resin composition comprising the same are aggregated due to more uniform dispersion of the fibrous filler during injection molding. It is to make it easy to suppress, and to suppress the generation of bright spots and flow marks, thereby making it easy to improve the molding appearance and physical property balance.
The term “strain hardenability” as used herein means that the elongational viscosity gradually increases as the amount of stretch strain of the melt increases. It is a case of increasing.

  Here, as to the method for evaluating strain hardening, any method can be used in principle as long as the uniaxial elongation viscosity can be measured. For example, details of the measuring method and measuring instrument are known: Polymer 42 (2001) 8663 is described as a preferred measuring method, but as a measuring device, Rheometrics Ales (Jig: Extensive Visibility Fixture manufactured by TEA Instruments), Toyo Seiki Co., Ltd., Melten The method using Rheometer is mentioned.

  The degree of strain hardening is 2.0 or more, more preferably 2.5 or more, particularly preferably 3.0 or more, further preferably 5 in the 180 ° C. extensional viscosity measurement (strain rate: 1.0 / sec). It preferably has a strain hardening degree (λmax) of 0.0 or more. When the strain hardening degree (λmax) satisfies the above range, the moldability, molding appearance and physical property balance can be expressed at a better level in the MB of the present invention, the resin composition comprising the same, injection molding and injection molding. .

Other characteristics:
The weight average molecular weight (Mw) of the linear ethylene / propylene random copolymer portion in the linear propylene / ethylene block copolymer used as necessary for the MB of the present invention is preferably 1,000,000 or more, more preferably Is 1.1 million to 8 million, more preferably 1.2 million to 7 million, and particularly preferably 1.5 million to 4 million.
In the MB of the present invention, the resin composition comprising the same, injection molding and injection molded article, the weight average molecular weight (Mw) should be in the above-mentioned range in order to make the molded appearance and physical property balance easier to express at a better level. preferable.

  The die swell ratio of the entire linear propylene / ethylene block copolymer used as necessary for the MB of the present invention is 1.2 to 2.5, preferably 1.3 to 2.4, more preferably 1 4 to 2.3. When the die swell ratio satisfies the above range, MB, a resin composition comprising the same, an injection molding and an injection molded article can exhibit a good molding appearance and physical property balance, and the industrial production of the block copolymer is stable. Is possible.

MFR and die swell ratio are measured with MFR meter, linear ethylene / propylene random copolymer portion content (constituent ratio), ethylene content, Q value and Mw, cross fractionation device, Fourier transform infrared absorption spectrum analysis These are values measured using gel permeation chromatography (GPC). Intrinsic viscosity [η] _copy is measured using an Ubbelohde viscometer, and strain hardening in 180 ° C. extension viscosity measurement is measured using an extension viscometer. The measurement conditions of main items are described in the examples.

(3) Production of Component A The production method of Component A used in the MB of the present invention has the above characteristics (i) to (vii in the linear propylene / ethylene block copolymer). As long as it is not particularly limited, it is appropriately selected from known methods and conditions.
As the propylene polymerization catalyst, a highly stereoregular catalyst is usually used, and examples thereof include a Ziegler catalyst and a metallocene catalyst.
For example, a catalyst comprising a combination of a titanium trichloride composition obtained by reducing titanium tetrachloride with an organoaluminum compound and further treating with various electron donors and electron acceptors, an organoaluminum compound and an aromatic carboxylic acid ester ( (See JP-A-56-100806, JP-A-56-120712, JP-A-58-104907), and a support in which titanium tetrachloride and various electron donors are brought into contact with magnesium halide. Type catalysts (see JP-A-57-63310, JP-A-63-43915, and JP-A-63-83116).

  In the presence of the catalyst, a production process such as a gas phase polymerization method, a liquid phase bulk polymerization method, or a slurry polymerization method is applied to polymerize propylene, or polymerize propylene, and then randomly polymerize propylene and ethylene. Is obtained. In order to obtain a propylene / ethylene block copolymer having the above-described melting characteristics (MFR), it is preferable to perform multistage polymerization by a slurry method or a gas phase fluidized bed method.

Here, the polymerization of the linear propylene polymer portion in the linear propylene / ethylene block copolymer may be one-stage polymerization or multi-stage polymerization of propylene, but exhibits the above characteristics. Therefore, it is more preferable to obtain by multistage polymerization.
Examples of the multistage polymerization method for the linear propylene polymer portion include a two-stage polymerization method by the following step (1) and step (2).

  Step (1): Propylene is polymerized in the presence of hydrogen as a molecular weight regulator. This is to suppress the formation of a polymer having a too high molecular weight. Hydrogen is added so that the MFR of the linear propylene polymer portion is 120 g / 10 min or more. The hydrogen concentration is usually selected from the range of 0.1 to 40 mol% with respect to the total monomer amount. The polymerization temperature is usually selected from the range of 40 to 90 ° C., and the pressure is usually selected from the range of 0.1 to 5 MPa. The amount of the polymer obtained in this step (1) is usually adjusted to be 80 to 99% by weight of the total polymerization amount. When the amount of the polymer produced in the step (1) is less than 80% by weight, the amount of the high molecular weight propylene polymer produced in the step (2) is excessively increased and the moldability is impaired.

  Step (2): Compared with the linear propylene polymer portion produced in Step (1), in order to polymerize a high-molecular-weight propylene polymer, the hydrogen atmosphere is as low as possible or is substantially free of hydrogen. It is preferable to polymerize with. The polymerization is subsequently carried out in the presence of the propylene polymer produced in step (1) and a catalyst. The polymerization temperature is usually selected from the range of 40 to 90 ° C., and the pressure is usually selected from the range of 0.1 to 5 MPa. The amount of the polymer obtained in this step (2) is usually adjusted to be 1 to 20% by weight of the total polymerization amount. Any combination may be adopted as long as the physical property value of the whole polymer obtained by combining the step (1) and the step (2) can be adjusted to the above-described range.

  The linear propylene polymer portion is preferably a homopolymer of propylene in order to increase the rigidity of the MB of the present invention, the resin composition comprising the same, and the injection-molded product. Thus, a copolymer with a small amount of a comonomer can be used as long as the crystallinity is not significantly impaired. Specifically, for example, α-olefins other than propylene such as ethylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl 1-pentene, styrene, vinylcyclopentene, vinyl A comonomer unit corresponding to one or more comonomers selected from the group consisting of vinyl compounds such as cyclohexane and vinyl norbornane, etc., can be contained preferably in a content of 5% by weight or less. Two or more of these comonomers may be copolymerized. The comonomer is preferably ethylene and / or 1-butene, most preferably ethylene. Here, the content of the comonomer unit is a value determined by infrared spectroscopy (IR).

Following the polymerization of the linear propylene polymer portion, the linear ethylene / propylene random copolymer portion is polymerized. The linear ethylene / propylene random copolymer portion is preferably a high molecular weight linear ethylene / propylene random copolymer in order to adjust the molecular weight distribution (Q value) and die swell ratio to predetermined values.
The polymerization of the linear ethylene / propylene random copolymer portion is preferably performed in a hydrogen atmosphere as low as possible or in a state substantially free of hydrogen in order to polymerize a high molecular weight polymer. The polymerization is carried out successively in the presence of the propylene polymer produced in the linear propylene polymer partial polymerization step and a catalyst. The polymerization temperature is usually selected from the range of 40 to 90 ° C., and the pressure is usually selected from the range of 0.1 to 5 MPa.

(4) Blending ratio of component A The blending ratio of component A in the MB of the present invention is 30 to 75 wt%, preferably 35 to 70 wt%, more preferably 40 to 65 wt% with respect to 100 wt% of the entire MB. % By weight.
When the blending ratio is less than 30% by weight, it is difficult to produce the MB of the present invention, and the physical properties such as moldability, molding appearance and impact strength of the MB, a resin composition comprising the same, and injection molding and injection molded products. descend. On the other hand, when it exceeds 75% by weight, physical properties such as rigidity decrease.

  Component A may be used singly or in combination of two or more. Among these, linear propylene / ethylene block copolymer is 30 to 100% by weight, preferably 50%, based on 100% by weight of Component A as a whole. ˜100% by weight and other propylene / ethylene block copolymers of 0 to 70% by weight, preferably 0 to 50% by weight, are MB of the present invention, resin composition comprising the same, injection molding and injection In the molded body, it is preferable in that the molded appearance and physical property balance are easily improved.

2. Fibrous filler (component B)
The fibrous filler (component B) used in the MB of the present invention is an excellent balance of physical properties such as rigidity and imparts dimensional stability in the MB of the present invention, a resin composition comprising the same, and injection molding and injection molded articles. It is used for the purposes of (reducing the linear expansion coefficient), providing compatibility with various required performances such as dimensions and physical properties, and reducing the weight of the molded product in terms of absolute weight and rigidity.

(1) Type, shape, etc. Component B types include basic magnesium sulfate fiber (magnesium oxysulfate fiber), potassium titanate fiber, aluminum borate fiber, calcium silicate fiber, calcium carbonate fiber, carbon fiber, glass fiber. , Wollastonite, zonotlite, various metal fibers, natural fibers such as cotton, silk, wool or hemp, regenerated fibers such as rayon or cupra, semi-synthetic fibers such as acetate and promix, polyester, polyacrylonitrile, polyamide, aramid, Examples thereof include synthetic fibers such as polyolefin.
Among these, basic magnesium sulfate fiber (magnesium oxysulfate fiber), potassium titanate fiber, aluminum borate fiber, calcium silicate fiber, calcium carbonate fiber, carbon fiber (small diameter), etc. (also called whisker) The fine fiber filler is the MB of the present invention, the resin composition comprising the same, injection molding and injection molded article, imparting molded appearance, physical property balance, dimensional stability (reducing linear expansion coefficient, etc.), dimensions and physical properties. From the standpoint of a large improvement effect such as adaptability to various required performances such as, basic magnesium sulfate fiber (magnesium oxysulfate fiber) is particularly preferable.

The average fiber diameter of component B is not particularly limited, but is preferably 2 μm or less, more preferably 1 μm or less, and particularly preferably 0.8 μm or less.
Also, the average fiber length is not particularly limited, but is preferably 100 μm or less, more preferably 0.5 μm to 50 μm, and particularly preferably 1 μm to 20 μm.
Furthermore, the component B may be used in the form of a compressed soul produced for the purpose of improving the mixing workability, a solidified granule or a granulated product.
These components B are various organic titanate coupling agents, organic silane coupling agents, unsaturated carboxylic acids, or anhydrides thereof for the purpose of improving adhesion or dispersibility with the component A. Surface-treated with a modified polyolefin grafted with a fatty acid, a fatty acid, a fatty acid metal salt, a fatty acid ester, or the like may be used.

  The production method of component B is not particularly limited, and is produced by various known production methods. For example, in the case of basic magnesium sulfate fiber (magnesium oxysulfate fiber), it is produced by a method such as hydrothermal synthesis using magnesium hydroxide and magnesium sulfate as raw materials.

(2) Blending ratio of component B The blending ratio of component B in the MB of the present invention is 25 to 70% by weight, preferably 30 to 65% by weight, more preferably 35 to 60%, based on 100% by weight of the whole MB. % By weight.
If the blending ratio is less than 25% by weight, the physical properties such as rigidity of the MB of the present invention, the resin composition comprising the same, injection molding and injection molding, dimensional stability, and the required performance and economic efficiency are reduced. To do. On the other hand, when it exceeds 70% by weight, it is difficult to produce the MB, and physical properties such as molding appearance and impact strength are lowered.
Component B may be used alone or in combination of two or more.

  Here, in the MB of the present invention, a resin composition comprising the same, injection molding and injection molded article, the development of excellent physical property balance such as rigidity and the provision of dimensional stability (reduction of linear expansion coefficient and relaxation of molding anisotropy) Talc, which is one type of non-fibrous filler described later, is 40 to 1000 parts by weight, preferably 50 to 500 parts by weight, more preferably 60 parts by weight per 100 parts by weight of component B. It is preferable to blend ~ 300 parts by weight. If the blending amount is less than 40 parts by weight, the above effects tend not to be obtained sufficiently, and if it exceeds 1000 parts by weight, the molded appearance tends to be lowered.

3. Fatty acid metal salt (component C)
The fatty acid metal salt (component C) used in the MB of the present invention mainly promotes the dispersion of the component B in the MB of the present invention, the resin composition comprising the same, and the injection molded product and injection molded product, For the purpose of suppressing the occurrence of the material, such as the appearance of excellent molding appearance (suppression of bright spot generation, etc.), the appearance of excellent physical properties such as rigidity, and the provision of dimensional stability (reduction of the linear expansion coefficient, etc.) Used.

(1) Kind, property, etc. Component C is a fatty acid metal salt or basic fatty acid metal salt represented by the following general formula (1) or general formula (2).
M (RCOO) _n (1)
mM ¹ O · M ² (RCOO) ₂ (2)
[Wherein R Is obtained by removing a carboxyl group from a saturated or unsaturated aliphatic monocarboxylic acid having 8 to 32 carbon atoms (preferably 10 to 22 carbon atoms) which may have one or more hydroxyl groups in the molecule. Represents a residue. n represents an integer of 1 or 2, and when n = 2, two Rs may be the same or different. M represents a metal belonging to Group 1, Group 2, Group 12, or Group 13 of the periodic table. M represents the excess number of moles of the metal oxide in the basic fatty acid metal salt represented by the formula (2), and M ¹ and M ² are metals belonging to Group 2 or Group 12 of the periodic table, respectively. It is. ]

Specifically, a saturated or unsaturated aliphatic monocarboxylic acid having 8 to 32 carbon atoms (preferably 10 to 22 carbon atoms) which may have one or more hydroxyl groups in the molecule, and a periodic table. It consists of metals belonging to Group 1, Group 2, Group 12 or Group 13.
Component C includes a compound or a mixture of the fatty acid metal salt or the basic fatty acid metal salt and a metal oxide or / and a metal hydroxide.

  As the aliphatic monocarboxylic acid in the above formula (1), caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, neodecanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, Margaric acid, oleic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, mellicic acid, succinic acid, lindelic acid, tuzic acid, palmitoleic acid, petraceric acid, elaidic acid, vacsen Examples thereof include acid, linoleic acid, linoelaidic acid, γ-linolenic acid, linolenic acid, ricinoleic acid, 12-hydroxystearic acid, naphthenic acid, and abietic acid. Preferably, at least one selected from lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, behenic acid, montanic acid and 12-hydroxystearic acid is used.

  Examples of the metal belonging to Group 1, Group 2, Group 12, or Group 13 of the periodic table in the above formula (1) include alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, strontium, barium). Etc.), magnesium, zinc, aluminum and the like, and preferably at least one selected from magnesium, calcium, zinc, lithium, sodium and potassium.

Preferred component C includes at least one aliphatic monocarboxylic acid selected from lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, behenic acid, montanic acid and 12-hydroxystearic acid, magnesium, calcium, Examples include fatty acid metal salts composed of at least one metal selected from zinc, lithium, sodium and potassium.
Specifically, magnesium palmitate, magnesium oleate, magnesium stearate, magnesium behenate, 12-hydroxy magnesium stearate, calcium stearate, calcium behenate, calcium 12-hydroxystearate, zinc stearate, zinc behenate, 12 -Zinc hydroxystearate, sodium stearate, sodium 12-hydroxystearate, potassium stearate, potassium 12-hydroxystearate, lithium stearate, lithium 12-hydroxystearate and the like.

Among them, particularly preferable component C is that in which the metal is composed of at least one metal selected from magnesium, calcium or zinc. Specifically, magnesium oleate, magnesium stearate, magnesium behenate, Examples include magnesium hydroxystearate, calcium oleate, calcium stearate, calcium behenate, calcium 12-hydroxystearate, zinc oleate, zinc stearate, zinc behenate, and zinc 12-hydroxystearate.
More preferable component C is one in which the metal is magnesium, and specific examples include magnesium oleate, magnesium stearate, magnesium behenate, and 12-hydroxy magnesium stearate.

The melting point of component C is not particularly limited. For example, when the metal is magnesium, the melting point is preferably 116 ° C. or higher, more preferably 120 ° C. or higher, and particularly preferably 125 ° C. or higher. When the melting point is less than 116 ° C., the dispersibility, physical property balance and molding appearance of Component B in the MB of the present invention, the resin composition comprising the same, and the injection molded product tend to be lowered.
For example, when the metal is calcium, the temperature is preferably 140 ° C. or higher, more preferably 142 ° C. or higher, and particularly preferably 145 ° C. or higher. When the melting point is less than 140 ° C., the dispersibility, physical properties and molded appearance tend to be lowered.
Furthermore, for example, when the metal is zinc, one having a temperature of 116 ° C. or higher is preferable, one having a temperature of 120 ° C. or higher is more preferable, and one having a temperature of 125 ° C. or higher is particularly preferable. When the melting point is less than 116 ° C., the dispersibility, physical properties and molded appearance tend to be lowered. Here, the melting point is a value measured using a differential scanning calorimeter or the like.

The content of each metal in component C is not particularly limited. For example, when the metal is magnesium, it is preferably 3.2% by mass or more, more preferably 3.6% by mass or more. Those having a mass% or more are particularly preferred. When the magnesium content is less than 3.2% by mass, the dispersibility, physical properties, and molded appearance of Component B in the MB of the present invention, the resin composition comprising the same, and the injection molded product tend to be lowered.
For example, when the metal is calcium, 5.0% by mass or more is preferable, 5.5% by mass or more is more preferable, and 6.0% by mass or more is particularly preferable. When the calcium content is less than 5.0% by mass, the dispersibility, physical properties and molded appearance tend to be lowered.
Furthermore, for example, when the metal is zinc, it is preferably 10.0% by mass or more, more preferably 10.4% by mass or more, and particularly preferably 11.0% by mass or more. When the zinc content is less than 10.0% by mass, the dispersibility, physical properties and molded appearance tend to be lowered. Here, the metal content is a value measured using a thermogravimetric measuring device or the like.

In these components C, it is particularly preferable to use the above basic fatty acid metal salt from the viewpoint of further improving the dispersibility of the component B mainly in the MB of the present invention, the resin composition comprising the same, and the injection molded article. preferable.
This basic fatty acid metal salt is obtained by reaction with an excess amount of a metal compound, and is represented by the above general formula (2) (re-described below).
mM ¹ O · M ² (RCOO) ₂ (2)
In the formula, m represents the excess number of moles of the metal oxide in the basic fatty acid metal salt represented by the formula (2) as described above. m is preferably from 0.1 to 2.0, more preferably from 0.1 to 1.0, particularly from 0.2 to 0.5, because the above-described dispersion effect is excellent. Is particularly preferred. If m is less than 0.1, the above-mentioned effect of improving the dispersion tends to be insufficient, and if it exceeds 2.0, the melting point of the basic fatty acid metal salt becomes too high, and the above-mentioned dispersion or the like is still present. The improvement effect tends to be insufficient.
M ¹ and M ² are metals belonging to Group 2 or Group 12 of the periodic table as described above, and they may be the same or different. Examples of such metals include magnesium, calcium, and zinc. Among them, magnesium is more preferable because it is excellent in the effect of improving the dispersion and the like.
RCOO represents a saturated or unsaturated fatty acid residue, and is preferably a saturated or unsaturated fatty acid residue having 12 to 22 carbon atoms because of excellent improvement effects such as dispersion.
Examples of such saturated or unsaturated fatty acid residues include lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, behenic acid, 12-hydroxystearic acid and the like.

  Examples of the basic fatty acid metal salt represented by the formula (2) used in the present invention include basic magnesium laurate, basic calcium laurate, basic zinc laurate, basic magnesium myristate, and basic zinc myristate. , Basic magnesium palmitate, basic zinc palmitate, basic magnesium stearate, basic calcium stearate, basic zinc stearate, basic 12-hydroxy magnesium stearate, basic 12-hydroxy calcium stearate, basic 12 -Zinc hydroxy stearate, basic magnesium behenate, basic zinc behenate, etc., among which basic magnesium stearate, basic zinc stearate, base, etc. Magnesium 12-hydroxystearic acid is preferably a basic 12-hydroxystearic acid zinc, basic magnesium stearate, and more preferably basic 12-hydroxystearic magnesium phosphate.

  The melting point of these basic fatty acid metal salts is not particularly limited. For example, when the metal is magnesium, the melting point is preferably 120 ° C. or higher, more preferably 125 ° C. or higher, and particularly preferably 130 ° C. or higher. When the melting point is less than 120 ° C., the effect of improving the dispersibility, physical properties and molding appearance of component B in the MB of the present invention, the resin composition comprising the same, and the injection molded article tends to be small.

  The metal content in the basic fatty acid metal salt is not particularly limited. For example, when the metal is magnesium, it is preferably 3.6% by mass or more, and preferably 3.8% by mass or more. More preferred is 4.0% by mass or more. When the magnesium content is less than 3.6% by mass, the effect of improving the dispersibility, physical properties, and molded appearance tends to be small.

The production method of component C used in the present invention is not particularly limited, but usually a metathesis method (wet method) or a direct method (dry method) is used. For example, the metathesis method (wet method) is a method in which a fatty acid alkali soap and a metal salt are reacted in water to produce a fatty acid metal salt by precipitation.
The direct method (dry method) is a method in which a fatty acid is directly reacted with a metal oxide or hydroxide. Here, these production methods have their respective characteristics, but if anything, the MB of the present invention, the resin composition comprising the same, and the effect of improving the dispersibility, physical properties and molding appearance of component B in the injection molded product. From the standpoint of superiority and the like (including basic fatty acid metal salts), it is preferable to produce them using a direct method (dry method).

(2) Blending ratio of component C The blending ratio of component C in the MB of the present invention is 0.01 to 10 parts by weight, preferably 0.05 to 8 with respect to 100 parts by weight of component A and component B in total. Part by weight, particularly preferably 0.1 to 5 parts by weight.
When the blending ratio is less than 0.01 parts by weight, component B is not sufficiently dispersed or aggregates of the component are generated in the MB of the present invention, the resin composition comprising the same, and injection molding and injection molded product. As a result, physical properties such as molding appearance (such as generation of bright spots) and impact strength deteriorate. On the other hand, when it exceeds 10 parts by weight, physical properties such as rigidity and heat resistance and economic efficiency are lowered.
Component C may be used alone or in combination of two or more.

[II] Constituent Components of Resin Composition The resin composition comprising the MB of the present invention comprises the above-mentioned MB and polypropylene resin (component D, hereinafter also simply referred to as component D), and elastomer (component E, hereinafter simply referred to as “component D”). Component E) and / or non-fibrous filler (component F, hereinafter also simply referred to as component F). Hereinafter, components other than MB will be described.

1. Polypropylene resin (component D)
Component D used in the resin composition comprising MB of the present invention is MB, and, if necessary, component E or / and component F in the resin composition, injection molding or injection molded product of MB of the present invention, It is a component that is mixed or kneaded, and is a component that imparts and develops moldability and strength in the resin composition, injection molding and injection molded body.
Component D is, for example, a propylene homopolymer, a copolymer of propylene and an α-olefin such as a propylene / ethylene random copolymer or a propylene / ethylene block copolymer, a copolymer of propylene and a vinyl compound, propylene Copolymer of styrene and vinyl ester, copolymer of propylene and unsaturated organic acid or derivative thereof, copolymer of propylene and conjugated diene, copolymer of propylene and non-conjugated polyene, and mixtures thereof Is mentioned.
Among these, a copolymer of propylene and ethylene is preferable, and a propylene / ethylene block copolymer is particularly preferable. The linear propylene / ethylene block copolymer is also one of the preferable ones.

The MFR (230 ° C., 2.16 kg load) of the entire component D is not particularly limited, but is preferably 1 to 500 g / 10 minutes, more preferably 5 to 300 g / 10 minutes, and particularly preferably 10 to 200 g / 10 minutes. More preferably, it is 20 to 100 g / 10 min.
When the MFR is less than 1 g / 10 min, the molded appearance tends to deteriorate in the resin composition comprising the MB of the present invention, the injection molded product and the injection molded product. Tends to decrease.
The production method of component D is not particularly limited, and is appropriately selected from known methods and conditions.

2. Elastomer (component E)
Component E used as necessary in the resin composition comprising MB of the present invention is a component that is mixed or kneaded with MB, component D, and optionally component F in the resin composition comprising MB of the present invention. Yes, it is used for imparting and improving impact strength, dimensional stability, and the like in the resin composition and injection molded article made of MB of the present invention.
Component E can also be used in the MB of the present invention to impart or improve the impact strength or dimensional stability of the MB itself.
Component E includes, for example, ethylene / propylene copolymer elastomer (ethylene propylene rubber; EPR), ethylene / butene copolymer elastomer (EBR), ethylene / hexene copolymer elastomer (EHR), and ethylene / octene copolymer elastomer. (EOR) and other ethylene / α-olefin copolymer elastomers; ethylene / propylene / ethylidene norbornene copolymers, ethylene / propylene / butadiene copolymers, ethylene / propylene / isoprene copolymers, etc. Diene terpolymer elastomer: styrene / butadiene / styrene triblock (SBS), hydrogenated styrene / butadiene / styrene triblock (SEBS), styrene / isoprene / styrene triblock (SI) S), and styrene-based elastomers such as hydrogenated products (SEPS) of styrene / isoprene / styrene triblock bodies.
Of these, ethylene / α-olefin copolymer elastomers are preferred, and ethylene / butene copolymer elastomers (EBR) and ethylene / octene copolymer elastomers (EOR) are particularly preferred.

The MFR (230 ° C., 2.16 kg load) of component E is not particularly limited, but is preferably 0.5 g / 10 min or more, more preferably 1.0 g / 10 min or more, and particularly preferably 2.0 g / 10. More than a minute.
When the MFR is less than 0.5 g / 10 min, the molded appearance tends to be deteriorated in the MB of the present invention, the resin composition comprising the same, injection molding and injection molded article.
The manufacturing method of the component E is not specifically limited, It selects suitably from well-known methods and conditions.

3. Non-fibrous filler (component F)
Component F used as needed in the resin composition comprising MB of the present invention is a component that is mixed or kneaded with MB, component D, and optionally component E in the resin composition comprising MB of the present invention. Yes, for imparting and improving physical properties such as rigidity and dimensional stability (reduction of linear expansion coefficient, relaxation of molding anisotropy, etc.), etc. in the resin composition and injection-molded body comprising MB of the present invention It is done.
Component F includes oxides such as silica and diatomaceous earth, hydroxides such as aluminum hydroxide and magnesium hydroxide, carbonates such as calcium carbonate and magnesium carbonate, sulfates or sulfites such as calcium sulfate and barium sulfate. Silicates such as talc, clay, mica and wollastonite, carbons such as carbon black, and granular wood powder.
Here, talc, in particular, talc having an average particle size of 15 μm or less, more preferably 0.5 to 10 μm, especially 2 to 8 μm, is excellent in balance of physical properties such as molding appearance, rigidity, dimensional stability, and economic efficiency. MB, a resin composition comprising the same, and an injection-molded product are preferable.
The average particle diameter is a value measured using a laser diffraction / scattering particle size distribution analyzer or the like, and examples of the measuring apparatus include Horiba LA-920 type. Further, talc having an average aspect ratio of 4 or more, particularly 5 or more is more preferable. The aspect ratio of talc is measured from a value measured with a microscope or the like.

The shape and size of the component F are not particularly limited, but in general, when the size such as the particle size is excessive for each type, in the resin composition and injection-molded body made of the MB of the present invention, the molded appearance, impact strength, etc. There is a tendency for the physical properties of to decrease.
The manufacturing method of the component F is not specifically limited, It selects suitably from well-known methods and conditions.

4). Blending ratio The blending ratio of MB, component D, component E and component F in the resin compositions of the seventh to eleventh inventions of the present invention is the ratio shown below.
(1) Resin composition of the seventh and tenth inventions (1-a) MB
The blending ratio of MB is preferably 2 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 8 to 30% by weight with respect to 100% by weight of the total of MB and component D. When the blending ratio is less than 2% by weight, physical properties such as rigidity and dimensional stability tend to be lowered in the resin composition and the injection-molded body made of MB of the present invention. On the other hand, when it exceeds 50% by weight, physical properties such as molding appearance and impact strength tend to decrease.

(1-b) Component D
The blending ratio of component D is preferably 50 to 98% by weight, more preferably 60 to 95% by weight, and particularly preferably 70 to 92% by weight with respect to 100% by weight of the total of MB and component D.
When the blending ratio is less than 50% by weight, physical properties such as molding appearance and impact strength tend to be lowered in the resin composition and injection-molded body made of MB of the present invention. On the other hand, when it exceeds 98% by weight, physical properties such as rigidity and dimensional stability tend to decrease.

(2) The resin composition of the eighth, ninth and eleventh inventions (2-a) MB
The blending ratio of MB is preferably 2 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 8 to 30% with respect to 100% by weight of the total of MB, component D, component E and / or component F. % By weight.
When the blending ratio is less than 2% by weight, physical properties such as rigidity tend to decrease in the resin composition and the injection-molded body made of MB of the present invention. On the other hand, when it exceeds 50% by weight, physical properties such as molding appearance and impact strength tend to decrease.

(2-b) Total of component D, component E or / and component F The total blending ratio of component D, component E and component F is 100% by weight in total of MB and component D, component E or / and component F Is preferably 50 to 98% by weight, more preferably 60 to 95% by weight, and particularly preferably 70 to 92% by weight.
When the blending ratio is less than 50% by weight, physical properties such as molding appearance and impact strength tend to be lowered in the resin composition and injection-molded body made of MB of the present invention. On the other hand, when it exceeds 98% by weight, physical properties such as rigidity tend to be lowered.

(2-c) The ratio of each component D to F with respect to the sum of component D, component E or / and component F The ratio of component D to the sum of component D, component E or / and component F is the ratio of component D, component E or / And 50% by weight or more is preferable with respect to the total of 100% by weight of Component F. Similarly, the proportion of Component E is preferably 2 to 40% by weight, and similarly the proportion of Component F is preferably 2 to 50% by weight. .
When the ratio of the component D to the total of the component D, the component E and / or the component F is less than 50% by weight, in the resin composition and the injection-molded body made of the MB of the present invention, the molding appearance, moldability, etc. are lowered. Tend. Similarly, if the proportion of component E is less than 2% by weight, physical properties such as impact strength tend to decrease, and if it exceeds 40% by weight, physical properties such as molding appearance and rigidity tend to decrease. Further, when the proportion of component F is less than 2% by weight, physical properties such as dimensional stability and rigidity tend to decrease, and when it exceeds 50% by weight, physical properties such as molding appearance and impact strength tend to decrease.

[III] Optional addition component (component G)
In the MB of the present invention and the resin composition comprising the same, in addition to the components A to F, if necessary, the effects of the present invention can be further improved, for example, within the range not significantly impairing the effects of the present invention. An optional additive component (component G, hereinafter also simply referred to as component G) can be blended to impart an effect.
Specifically, colorants such as pigments, light stabilizers such as hindered amines, UV absorbers such as benzotriazoles, antioxidants such as phenols and phosphoruss, chemicals such as sodium bicarbonate and citric acid, and carbonic acid Gas, nitrogen and other physical foaming agents, sorbitol nucleating agents, nonionic antistatic agents, dispersants other than the component C, fatty acid amide based lubricants, neutralizing compounds such as inorganic compounds Antibacterial and antifungal agents such as thiazoles, flame retardants such as halogen compounds, process oils (formulated oils), plasticizers, metal deactivators such as nitrogen compounds, nonionic surfactants, and the above component A Polyolefins such as polypropylene, thermoplastic resins such as polyamide and polyester, elastomers (rubbers) other than component E, and resins other than component B and component F Or the like can be mentioned error. These components may be used in combination of two or more, may be added to the composition, may be added to each of the components, or may be used in combination of two or more in each component.

Examples of the colorant include titanium oxide; iron oxide (eg, bengara); chromic acid (eg, chrome lead); molybdic acid; selenide sulfide; ferrocyanide and carbon black, and other inorganic pigments. Soluble azo chelates; Insoluble azo chelates; Condensable azo chelates; Other azo chelates such as azo chelates; Phthalocyanine blue; Phthalocyanine pigments such as phthalocyanine green; Anthraquinone; Perinone; Perylene; Thylene pigments such as thioindigo; Dye lake; Organic pigments such as dioxazine-based; isoindolinone-based; Moreover, in order to make a metallic tone and a pearl tone, it can be used by containing an aluminum flake; a pearl pigment, and can also contain a dye.
These colorants are effective for imparting and improving the colored appearance, appearance, texture, commercial value, weather resistance, durability, and the like in the MB of the present invention, the resin composition comprising the same, and the injection molded article.

Examples of the light stabilizer and ultraviolet absorber include condensates 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] hexa Methylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]]; tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxyl Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate; bis (1,2,2,6,6-pentamethyl-4-piperidyl) Sebakei Hindered amine compounds such as bis-2,2,6,6-tetramethyl-4-piperidyl sebacate, and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5 -Chlorobenzotriazole; benzotriazoles such as 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone; Examples include benzophenone series such as 2-hydroxy-4-n-octoxybenzophenone, 4-t-butylphenyl salicylate; 2,4-di-t-butylphenyl 3 ′, 5′-di-t-butyl-4 Salicylates such as' -hydroxybenzoate are mentioned.
These light stabilizers and ultraviolet absorbers are effective for imparting and improving weather resistance, heat stability, durability, etc. in the MB of the present invention, resin compositions comprising the same, and injection molded articles.

Furthermore, examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol; tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate. ] -Methane; phenolic antioxidants such as tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, distearyl pentaerythritol diphosphite; tris (2,4-di- t-butylphenyl) phosphite; phosphorus-based antioxidants such as tris (2-t-butyl-4-methylphenyl) phosphite; and sulfur-based antioxidants such as distearyl thiodipropionate. .
These antioxidants are effective for imparting and improving heat stability, processing stability, heat aging resistance and the like in the MB of the present invention, resin compositions comprising the same, and injection molded articles.

[IV] Polypropylene masterbatch (MB) containing fibrous filler, resin composition comprising the same, method for producing injection molded product (injection molding method) and application Manufacturing method (1) MB
The MB production method of the present invention includes, for example, the component A, the component B and the component C, and further blends talc or / and the component G as necessary at the above blending ratio, and a single screw extruder, a twin screw extruder, Examples of the method include kneading and granulating using a Banbury mixer, roll mixer, stirring (blade) mixer, Brabender plastograph, kneader and the like, and in particular, kneading and granulating using a twin screw extruder. It is preferable to do this.
In this kneading and granulation, the blends of the above components A to C (optionally further talc or / and component G) may be kneaded at the same time, and each component is divided to improve performance. For example, a part or all of the component A and the component G can be first kneaded, and then the remaining components can be kneaded and granulated.
In kneading and granulating, component B or, in some cases, talc is preferably supplied and kneaded after melting component A or component G in order to reduce or prevent breakage of the component B, for example, an extrusion cylinder of a kneader. It is preferable to carry out the method by appropriately supplying them from the middle.

(2) Resin Compositions of Seventh to Eleventh Inventions The production method of the resin composition of the seventh to eleventh inventions of the present invention includes, for example, the MB and component D, and optionally component E or / and component F as necessary. (Each pellet, powder, etc.) and component G are blended in the above blending ratio, dry blended such as by hand blending, or mixed using various blenders such as V blenders and tumbler mixers, mixers, etc. It is done.
In addition, as a production method for kneading and granulating, the above components are blended in the above blending ratio, and a single screw extruder, a twin screw extruder, a Banbury mixer, a roll mixer, a stirring (blade) mixer, a Brabender plastograph, The method performed using kneaders, such as a kneader, can be mentioned.
In these methods, MB and component D, and further, if necessary, a mixture of component E or / and component F and component G may be mixed or kneaded and granulated simultaneously, and each component may be improved to improve performance. For example, it is also possible to first mix or knead and granulate part or all of MB and component D, and then knead and granulate the remaining components.

In the methods for producing the resin compositions of the seventh to eleventh inventions, MB is mixed with component D and a resin composition obtained by mixing or kneading component E or / and component F and component G as necessary. Alternatively, the resin composition can be obtained by kneading.
Among them, a resin composition obtained by mixing MB and a resin composition in which component D and component E or / and component F and component G are kneaded in advance is a resin composition in which MB and the same component are kneaded. Compared to materials, the number of heat histories during processing and the chance of breakage of component B can be reduced (breakage can be reduced or prevented), and the balance of physical properties can be improved.

  Here, a resin composition obtained by kneading or mixing MB and a resin composition in which component D and component E or / and component F and component G are kneaded in advance is a kneading ratio of MB and the resin composition. Alternatively, by finely adjusting the mixing ratio, the dimensions (molding shrinkage ratio), molding appearance and physical properties (rigidity, impact strength, etc.), etc. of the resin composition comprising the MB of the present invention and the injection molded article can be finely adjusted. It is possible to respond to various required performances from the market.

  The resin composition obtained by kneading the component D and the component E or / and the component F and the component G in advance as described above has a screw diameter of 250 mm or more used in a large-size facility excellent in production efficiency and economy, More preferably, melt kneading is preferably performed using a kneader of 280 mm or more, more preferably 300 mm or more. When a small and medium-sized kneader with a screw diameter of less than 250 mm is used, the production efficiency and economic efficiency of the MB of the present invention, the resin composition comprising the same, and the injection molded product tend to be lowered.

(3) Injection molded body (injection molding method)
Examples of the production method (injection molding method) for producing the injection molded product in the present invention include an injection molding method using a normal injection molding machine, an injection compression molding machine, or the like.
As an injection molding method, for example, MB and a resin composition (a pellet thereof) kneaded in advance with component D and optionally component E or / and component F and component G are mixed in advance or simultaneously mixed and injected. Examples include a method of supplying to a molding machine, heating and melting, and injection filling into a mold cavity and molding.

2. Uses The resin composition comprising the MB of the present invention and the use of an injection-molded product are excellent in molding appearance and have a great influence on physical properties and appearance (before molding). In order to reduce the chance of breakage, the balance of physical properties is good, the effect of improving economy is great, and the compatibility with various required performances such as dimensions and physical properties is excellent, so trims, instrument panels, pillars, various housings, Examples include automobile interior and exterior parts such as fenders, bumpers, trunks, etc., home appliance parts such as televisions, electronic product parts, various industrial parts, and building material 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) MFR:
Conforms to JIS-K7210. Test temperature: 230 ° C., load: 2.16 kg. However, the test pieces of Examples 5 to 9 and Comparative Examples 3 to 5 were cut out pellets from molded sheets.

(2) Agglomerates:
One MB pellet obtained is molded into a sheet-like test piece having a thickness of about 0.1 mm under the condition of heating at 230 ° C. for 3 minutes using a press molding machine. The presence or absence of agglomerates in the central 1 cm square was observed and evaluated in the following two stages.
○: Agglomerates are not recognized ×: Agglomerates are partly or numerous

(3) Molding appearance:
(3-a) Bright spot:
An injection molded body (120 mm × 120 mm × 3 mmt) sheet with wrinkles (height 100 μm, granular) is injection molded at a molding temperature of 210 ° C. with an injection molding machine with a clamping pressure of 170 tons.
The appearance of bright spots on the textured surface (ease of conspicuousness) was visually observed and evaluated in the following three stages.
○: Bright spot is not recognized △: Bright spot is partially recognized but it is hardly noticeable ×: Bright spot is recognized entirely or partially recognized and it is clearly noticeable In this case, ○ and △ Is a level that is judged to have practicality.

(3-b) Flow mark:
With the above injection molding machine, a 350 mm × 100 mm × 2 mmt sheet is injection molded at a molding temperature of 210 ° C. using a mold having a film gate with a width of 2 mm on the short side.
The occurrence of flow marks on the sheet surface was visually observed and evaluated in the following three stages.
○: The flow mark is not recognized or is partially recognized △: The flow mark is partially recognized but it is not conspicuous ×: The flow mark is recognized entirely or partially recognized and is conspicuous In this case, ◯ and Δ are levels that are judged to have practicality.

(4) Rigidity (flexural modulus):
Conforms to JIS-K7171. Test temperature: 23 ° C

(5) Izod impact strength (notched):
Conforms to JIS-K7110. Test temperature: 23 ° C

(6) Content (constituent ratio) of linear ethylene / propylene random copolymer portion and ethylene content:
(6-a) Analyzer used:
(I) Cross sorter:
Diamond Instruments CFC T-100 (abbreviated as CFC)
(Ii) Fourier transform infrared absorption spectrum analysis:
FT-IR, Perkin Elmer 1760X
The fixed wavelength infrared spectrophotometer attached as a CFC detector is removed, and an FT-IR is connected instead, and this FT-IR is used as a detector. The transfer line from the outlet of the solution eluted from the CFC to the FT-IR is 1 m long, and the temperature is maintained at 140 ° C. throughout the measurement. The flow cell attached to the FT-IR has an optical path length of 1 mm and an optical path width of 5 mmφ, and the temperature is maintained at 140 ° C. throughout the measurement.
(Iii) Gel permeation chromatography (GPC):
The GPC column in the latter part of the CFC is used by connecting three AD806MS manufactured by Showa Denko KK in series.

(6-b) CFC measurement conditions:
(I) Solvent: orthodichlorobenzene (ODCB)
(Ii) Sample concentration: 4 mg / mL
(Iii) Injection volume: 0.4 mL
(Iv) Crystallization: The temperature is lowered from 140 ° C. to 40 ° C. over about 40 minutes.
(V) Sorting method:
The fractionation temperature at the time of temperature-raising elution fractionation is 40, 100, and 140 ° C., and fractionation is performed in three fractions in total. In addition, the elution ratio (unit:% by weight) of the component eluting at 40 ° C. or lower (fraction 1), the component eluting at 40 to 100 ° C. (fraction 2), and the component eluting at 100 to 140 ° C. (fraction 3), respectively W ₄₀ , W ₁₀₀ , and W ₁₄₀ are defined. W ₄₀ + W ₁₀₀ + W ₁₄₀ = 100. Moreover, each fractionated fraction is automatically transported to the FT-IR analyzer as it is.
(Vi) Solvent flow rate during elution: 1 mL / min

(6-c) FT-IR measurement conditions:
After elution of the sample solution starts from GPC at the latter stage of CFC, FT-IR measurement is performed under the following conditions, and GPC-IR data is collected for each of the above-described fractions 1 to 3.
(I) Detector: MCT
(Ii) Resolution: 8 cm ⁻¹
(Iii) Measurement interval: 0.2 minutes (12 seconds)
(Iv) Number of integrations per measurement: 15 times

(6-d) Post-processing and analysis of measurement results:
The elution amount and molecular weight distribution of the components eluted at each temperature are determined using the absorbance at 2945 cm ⁻¹ obtained by FT-IR as a chromatogram. The elution amount is normalized so that the total elution amount of each elution component is 100%. Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene.
The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.

A calibration curve is created by injecting 0.4 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method. Conversion to molecular weight uses a general-purpose calibration curve with reference to “Size Exclusion Chromatography” written by Sadao Mori (Kyoritsu Shuppan). The following numerical values are used for the viscosity equation ([η] = K × M ^α ) used at that time.
(I) When creating a calibration curve using standard polystyrene:
K = 0.000138, α = 0.70
(Ii) When measuring a sample of a linear propylene / ethylene block copolymer:
K = 0.000103, α = 0.78
The ethylene content distribution (distribution of ethylene content along the molecular weight axis) of each eluted component is a ratio of the absorbance of 2956 cm ⁻¹ and the absorbance of 2927 cm ⁻¹ obtained by FT-IR, and is obtained by using polyethylene, polypropylene, or ¹³ Converted to ethylene content (% by weight) using a calibration curve prepared in advance using ethylene-propylene rubber (EPR) and mixtures thereof whose ethylene content is known by C-NMR measurement, etc. Ask.

(6-e) Content (constituent ratio) of linear ethylene / propylene random copolymer portion:
The content (Wc) of the ethylene / propylene random copolymer portion in the linear propylene / ethylene block copolymer used in the present invention is theoretically defined by the following formula (I). Desired.
Wc (% by weight) = W ₄₀ × A ₄₀ / B ₄₀ + W ₁₀₀ × A ₁₀₀ / B ₁₀₀ (I)
In the formula (I), W ₄₀ and W ₁₀₀ are elution ratios (unit:% by weight) in each of the above-described fractions, and A ₄₀ and A ₁₀₀ are actual values in the respective fractions corresponding to W ₄₀ and W _100. The measured average ethylene content (unit: wt%), and B ₄₀ and B ₁₀₀ are the ethylene content (unit: wt%) of the linear ethylene / propylene random copolymer portion contained in each fraction. . A method for _obtaining A ₄₀ , A ₁₀₀ , B ₄₀ , and B ₁₀₀ will be described later.

The meaning of the formula (I) is as follows. That is, the first term on the right side of the formula (I) is a term for calculating the amount of the linear ethylene / propylene random copolymer portion contained in the fraction 1 (portion soluble at 40 ° C.). When fraction 1 contains only a linear ethylene / propylene random copolymer and no linear propylene polymer, W ₄₀ is the linear ethylene / propylene random derived from fraction 1 as it is Fraction 1 contributes to the copolymer content, but in addition to the component derived from the linear ethylene / propylene random copolymer, a small amount of the component derived from the linear propylene polymer (component with extremely low molecular weight) And atactic polypropylene), it is necessary to correct the portion. Therefore, by multiplying W ₄₀ by A ₄₀ / B ₄₀ , the amount derived from the linear ethylene / propylene random copolymer portion in fraction 1 is calculated. For example, when the average ethylene content (A ₄₀ ) of fraction 1 is 30% by weight and the ethylene content (B ₄₀ ) of the linear ethylene / propylene random copolymer contained in fraction 1 is 40% by weight In the fraction 1, 30/40 = 3/4 (ie, 75% by weight) is derived from a linear ethylene / propylene random copolymer, and 1/4 is derived from a linear propylene polymer. Thus, the operation of multiplying A ₄₀ / B ₄₀ by the first term on the right side means that the contribution of the linear ethylene / propylene random copolymer is calculated from the weight% of fraction 1 (W ₄₀ ). The same applies to the second term on the right side. For each fraction, the linear ethylene / propylene random copolymer partial content is calculated by adding the contribution of the linear ethylene / propylene random copolymer. .

(I) As described above, the average ethylene contents corresponding to fractions 1 and 2 obtained by CFC measurement are A ₄₀ and A ₁₀₀ , respectively (unit is weight%). A method for obtaining the average ethylene content will be described later.

(Ii) The ethylene content corresponding to the peak position in the differential molecular weight distribution curve of fraction 1 is defined as B ₄₀ (unit is% by weight). Fraction 2 is considered to be substantially defined as B ₁₀₀ = 100 in the present invention because it is considered that the rubber part is completely eluted at 40 ° C. and cannot be defined with the same definition. B ₄₀ and B ₁₀₀ are the ethylene content of the linear ethylene / propylene random copolymer portion contained in each fraction, but it is practically impossible to obtain this value analytically. This is because there is no means for completely separating and fractionating the linear propylene polymer and the linear ethylene / propylene random copolymer mixed in the fraction.
As a result of examination using various model samples, B ₄₀ can explain the improvement effect of material physical properties well by using the ethylene content corresponding to the peak position of the differential molecular weight distribution curve of fraction 1. all right. Further, B ₁₀₀ has crystallinity derived from an ethylene chain, and the amount of linear ethylene / propylene random copolymer contained in these fractions includes linear ethylene / propylene random copolymer contained in fraction 1. For the two reasons that it is relatively small compared to the amount of coalescence, the approximation to 100 is closer to the actual situation and hardly causes an error in calculation. Therefore, the analysis is performed with B ₁₀₀ = 100.

(Iii) For the above reasons, the content (Wc) of the linear ethylene / propylene random copolymer portion is determined according to the following formula (II).
Wc _{(wt%) = W 40 × A 40} / B 40 + W 100 × A 100/100 ... (II)
That is, W ₄₀ × A ₄₀ / B ₄₀ which is the first term on the right side of the formula (II) indicates the content (wt%) of the linear ethylene / propylene random copolymer having no crystallinity, and the second term W ₁₀₀ × A _100/100 is a linear ethylene / propylene random copolymer partial content (% by weight) having crystallinity.
_Here, the average ethylene content _A 40 of _{B 40} and each of the fractions obtained by the CFC measurement 1 and _{2, A 100} is determined as follows.
Ethylene content corresponding to the peak position of the differential molecular weight distribution curve is B _40. In addition, the sum of the products of the weight ratio for each data point and the ethylene content for each data point, which is captured as data points at the time of measurement, is the average ethylene content A _{40 of} fraction 1. The average ethylene content A _{100 of} fraction 2 is determined in the same manner.

The significance of setting the three types of fractionation temperatures is as follows. In the CFC analysis of the present invention, a polymer having no crystallinity at 40 ° C. (for example, most of the linear ethylene / propylene random copolymer or extremely low molecular weight in the linear propylene polymer portion) It has the meaning that it is a temperature condition necessary and sufficient for fractionating only the component and the atactic component). 100 ° C. is a component that is insoluble at 40 ° C. but becomes soluble at 100 ° C. (for example, in a linear ethylene / propylene random copolymer, it has crystallinity due to the chain of ethylene and / or propylene) The temperature is necessary and sufficient to elute only the components and the linear propylene polymer having low crystallinity. 140 ° C. means a component that is insoluble at 100 ° C. but becomes soluble at 140 ° C. (for example, a component having particularly high crystallinity in a linear propylene polymer and a linear ethylene / propylene random copolymer) The temperature is necessary and sufficient to elute only the component having extremely high molecular weight and extremely high ethylene crystallinity and recover the entire amount of propylene / ethylene block copolymer used for analysis. W ₁₄₀ does not contain any linear ethylene / propylene random copolymer portion, or even if it is present, it is extremely small amount and can be substantially ignored. It is excluded from the calculation of the content of the polymer and the ethylene content of the linear ethylene / propylene random copolymer.

(6-f) Ethylene content of linear ethylene / propylene random copolymer portion:
The ethylene content of the linear ethylene / propylene random copolymer portion in the linear propylene / ethylene block copolymer used in the present invention is determined from the following formula using the values described above.
Ethylene content (% by weight) of linear ethylene / propylene random copolymer portion = (W ₄₀ × A ₄₀ + W ₁₀₀ × A ₁₀₀ ) / Wc
[Wc is the ratio (% by weight) of the linear ethylene / propylene random copolymer portion determined previously. ]

(7) Intrinsic viscosity [η] _{copy of the} linear ethylene / propylene random copolymer portion:
The intrinsic viscosity [eta] _copoly of linear ethylene-propylene random copolymer portion in the linear propylene-ethylene block copolymer used in the present invention is determined as follows.
First, after completion of the polymerization of the linear propylene polymer part, a part is sampled from the polymerization tank, and the intrinsic viscosity [η] _{homo of the part} is measured. Next, after polymerizing the linear propylene polymer portion, the intrinsic viscosity [η] _F of the final polymer (F) obtained by polymerizing the linear ethylene / propylene random copolymer portion is measured. This measurement is performed at a temperature of 135 ° C. using decalin as a solvent using an Ubbelohde viscometer. [Η] _copy is obtained from the following relationship.
[Η] _F = (100−Wc) / 100 × [η] _homo + Wc / 100 × [η] _copy

(8) Q value (Mw / Mn):
The Q value of the linear propylene / ethylene block copolymer used in the present invention is a value obtained by synthesizing the molecular weight distribution curves of fractions 1 to 3 measured by gel permeation chromatography in the aforementioned cross fractionator. It is determined from the molecular weight distribution curve of the whole chain propylene / ethylene block copolymer. The method for calculating the weight average molecular weight (Mw) and the number average molecular weight (Mn) from this molecular weight distribution curve is according to a known method, and Mw / Mn is used as the Q value.

(9) Strain hardenability:
The strain hardening property of the linear propylene / ethylene block copolymer used in the present invention is measured by the following method.
(9-a) Apparatus: Ales manufactured by Rheometrics
(9-b) Jig: EXTENSIONAL VISUALITY FIXTURE, manufactured by TA Instruments
(9-c) Test temperature: 180 ° C
(9-d) Strain rate: 1.0 / sec
(9-e) Sample test piece: press-molded sheet of 15 mm × 10 mm, thickness 0.5 mm

(9-f) Determination of presence or absence of strain hardening:
The elongational viscosity at a strain rate of 1.0 / sec is plotted as a logarithmic graph of the amount of strain on the horizontal axis and the elongational viscosity ηE (Pa · s) on the vertical axis. As the amount of strain increases, the extensional viscosity gradually increases, and when the rate of increase in the extensional viscosity increases abruptly from a certain amount of strain, this is a case where strain hardening is exhibited. The case was made “strain hard”. On the other hand, the case where the above-mentioned phenomenon was not substantially recognized was set as “no strain”.
(9-g) Calculation method of strain hardening degree (λmax):
On the above logarithmic graph, the viscosity immediately before the strain hardening is approximated by a straight line, and the maximum value (ηmax) of the elongational viscosity η _E until the strain amount becomes 4.0 is obtained. Let ηlin be the viscosity on the approximate straight line. ηmax / ηlin is defined as λmax.
The strain rate can be measured in the range of 0.001 / sec to 10.0 / sec, and the strain hardening degree varies depending on the difference in strain rate.

(10) Weight average molecular weight (Mw) of the linear ethylene / propylene random copolymer portion:
The weight average molecular weight (Mw) of the linear ethylene / propylene random copolymer portion in the linear propylene / ethylene block copolymer used in the present invention is measured by gel permeation chromatography in the cross fractionator. Obtained from the molecular weight distribution curve of fraction 1.

(11) Die swell ratio:
The die swell ratio of the linear propylene / ethylene block copolymer used in the present invention is a value determined by the following method.
Set the in-cylinder temperature of the MFR meter to 190 ° C. The orifice has a length of 8.00 mm, a diameter of 1.00 mmφ, and L / D = 8. Also, place a graduated cylinder containing ethyl alcohol directly under the orifice (the distance between the orifice and the ethyl alcohol liquid surface is 20 ± 2 mm). In this state, the sample is put into the cylinder, and the load is adjusted so that the extrusion amount per minute becomes 0.10 ± 0.03 g. The extrudate after 6 to 7 minutes is dropped into ethanol and solidified before being collected. The maximum and minimum values of the diameter of the strand-shaped sample of the collected extrudate were measured at 3 locations, 1 cm from the top, 1 cm from the bottom, and the center. Ratio.
The die swell ratio of the linear propylene / ethylene block copolymer can be determined, for example, in a hydrogen atmosphere at a concentration as low as possible or substantially in the presence of hydrogen during the polymerization of the constituent linear ethylene / propylene random copolymer portion. The polymerization can be carried out in such a state that the molecular weight is controlled to be high.

2. Material (1) Component A:
(1-a) A-1: Polymerized with Ziegler-based catalyst, linear propylene polymer portion MFR (230 ° C., 2.16 kg load) is 300 g / 10 min, linear ethylene / propylene random copolymer ratio is 7.4 wt% to the whole component a-1 parts, the intrinsic viscosity _{[eta] copoly} is 7.2dl / g, linear ethylene-propylene random copolymerization of linear ethylene-propylene random copolymer portion The ethylene content of the combined part is 35% by weight (measured by a cross fractionation method), the MFR of the whole component A-1 (230 ° C., 2.16 kg load) is 105 g / 10 minutes, and the Q value of the whole component A-1 is 8.1. , Exhibiting strain-hardening property at 180 ° C. extensional viscosity measurement (strain-hardening property “Yes”), strain hardening degree (λmax) is 3.73, and linear ethylene / propylene random copolymer portion Mw of 1.24 million (cross fractionation GPC measurement), linear propylene-ethylene block copolymer of the die swell ratio of the entire component A-1 1.6 (antioxidant-neutralizing agent, added already pellets).
(1-b) A-2: Propylene / ethylene block copolymer (antioxidant / neutralizing agent, added pellets) with an MFR (230 ° C., 2.16 kg load) of the entire component A-2 of 60 g / 10 min ).
(1-c) A-3: Propylene homopolymer (antioxidant / neutralizing agent, added pellets) of 300 g / 10 min of MFR (230 ° C., 2.16 kg load) of the entire component A-3.

(2) Component B:
(2-a) B-1: Basic magnesium sulfate fiber having an average fiber diameter of 0.5 μm, an average fiber length of 10 μm, and a true specific gravity of 2.3 (whisker-shaped fibers consolidated into granules) (Manufactured by Ube Materials)

(3) Component C:
(3-a) C-1: In the general formula (2), m = 0.12, M ¹ , M ² = Mg, RCOO = stearic acid, melting point = 140 ° C., magnesium content = 4.7 Basic magnesium stearate manufactured by the direct method (dry method) of mass%.
(3-b) C-2: In the general formula (2), m = 0.44, M ¹ , M ² = Mg, RCOO = stearic acid, melting point = 163 ° C., magnesium content = 5.7. Basic magnesium stearate manufactured by the direct method (dry method) of mass%.
(3-c) C-3: erucic acid amide

(4) Resin:
(4-a) Resin-1: The blending ratio is as follows: propylene / ethylene block copolymer = 85 wt% as component D, ethylene / butene copolymer elastomer = 15 wt% as component E, and resin-1 as a whole MFR (230 ° C., 2.16 kg load) of 40 g / 10 min, melt-kneaded (granulated) resin composition (antioxidant / neutralizing agent, added pellets) with a screw diameter of 320 mm ).
(4-b) Resin-2: blending ratio of component D as propylene / ethylene block copolymer = 69% by weight, component E as ethylene / butene copolymer elastomer = 15% by weight, component F as average particle size 5 Melting and kneading (granulation) in a kneader with a screw diameter of 320 mm, talc of .9 μm = 16 wt%, MFR of resin-2 as a whole (230 ° C., 2.16 kg load) is 37 g / 10 min. Resin composition (antioxidant / neutralizer, added pellets).

(Examples 1-4, Comparative Examples 1 and 2)
1. Production of Master Batch (MB) The above components A, B and C are blended in the proportions shown in Table 1, kneaded and granulated under the following conditions, and MB-I to IV (Examples 1 to 4). ) And MB-V, VI (Comparative Examples 1 and 2) were obtained.
In this case, component B and component C were supplied from the middle of the extruder cylinder (after melting of component A). The performance (MFR, agglomerate) evaluation results are also shown in Table 1.
(1) Kneading granulation conditions:
(1-a) Kneading apparatus: “TEX30α” type twin screw extruder manufactured by Nippon Steel Works.
(1-b) Kneading conditions: temperature = 210 ° C., discharge = 20 kg / H, screw rotation speed = 800 rpm, midway supply screw rotation speed = 480 rpm.

(Examples 5-9, Comparative Examples 3-5)
1. Production and Performance Evaluation of Resin Composition MB-I to VI obtained in Examples 1 to 4 and Comparative Examples 1 and 2, and the above resin-1 and resin-2 were mixed in the ratio shown in Table 2. A resin composition was produced and injection molded under the following conditions to evaluate its performance. However, Comparative Example 5 uses component A, component B and component C corresponding to MB-I as an alternative to the master batch (MB), and resin-1 under the same conditions (component B). And component C were fed in the middle) and injection molded. The evaluation results are shown in Table 3.
(1) Injection molding conditions:
(1-a) Injection molding machine: “IS100FB” type manufactured by Toshiba Machine Co., Ltd.
(1-b) Molding conditions: Molding temperature = 220 ° C., mold temperature = 35 ° C., injection rate = 42 cm ³ / sec.

  From the results shown in Tables 1 to 3, the resin composition and the injection-molded body composed of the fibrous filler-containing polypropylene masterbatch having the composition shown in Examples 5 to 9 satisfying the respective regulations in the essential constituent elements of the present invention, All have good molding appearance, physical properties (rigidity, impact strength) and fluidity (moldability). In addition to the above-mentioned various performances, they also have a large economic improvement effect and are excellent in compatibility with various required performances such as dimensions and physical properties. It has become apparent that it has suitable performance for industrial parts, building material parts, preferably automotive interior and exterior parts, especially trims, instrument panels, pillars, various housings, fenders, bumpers, trunks and the like.

On the other hand, the linear polypropylene resin compositions and injection-foamed molded articles having the compositions shown in Comparative Examples 3 to 5 are inferior due to their poor performance balance.
For example, in Comparative Example 3 using MB-V not containing Component C (Comparative Example 1), both the molded appearance and physical properties were significantly different from Example 1. This indicates that the effect of improving the molding appearance and physical properties varies significantly depending on whether or not the component C is contained, and it is essential that the component C satisfies the requirements of the present invention.
Further, in Comparative Example 4 using MB-VI containing C-3 as Component C, the molding appearance (bright spot) was significantly different from Example 1 in spite of the good molding appearance (flow mark). Occurred. This indicates that the effect of improving the molding appearance (bright spot) is significantly different due to the difference in component C, and it is essential that component C satisfies the requirements of the present invention.
Further, in Comparative Example 5 in which MB was not used and MB equivalent components and Resin-1 were melt-kneaded and then injection-molded, although the fluidity was good, the molding appearance (bright spot) was significantly different from Example 1. Differences occurred and physical properties also differed. This indicates that the effect of improving the molded appearance and the like is remarkably different depending on whether or not MB composed of components A to C is used, and the use of MB is essential.
From the results of the above examples and comparative examples, the rationality and significance of the configuration and requirements of the present invention are demonstrated, and the superiority of the present invention over the prior art is also apparent.

  The fibrous filler-containing polypropylene masterbatch of the present invention, a resin composition comprising the same, and an injection-molded product have good molding appearance, physical properties (rigidity, impact strength) and fluidity (moldability), as well as economy. It has a great effect on improving performance and is excellent in adaptability to various required performances such as dimensions and physical properties, so it can be used for automobile parts, home appliance parts such as TV sets, electronic product parts, various industrial parts, building material parts, preferably automobile interior and exterior. It can be suitably used for parts, especially trims, instrument panels, pillars, various housings, fenders, bumpers, trunks and the like.

Claims (11)

30 to 75% by weight of propylene-based resin (component A), 25 to 70% by weight of fibrous filler (component B), 0.01 to 100 parts by weight in total of fatty acid metal salt (component C) component A and component B A fibrous filler-containing polypropylene masterbatch containing 10 parts by weight ,
The propylene resin (component A) is at least partially composed of a linear propylene polymer portion and a linear ethylene / propylene random copolymer portion, and has the following characteristics (i) to (vii). A linear propylene / ethylene block copolymer, and
A fibrous filler-containing polypropylene masterbatch, wherein the fibrous filler (component B) is fibrous basic magnesium sulfate having an average fiber diameter of 2 μm or less and an average fiber length of 100 μm or less.
Characteristic (i): The melt flow rate (230 ° C., 2.16 kg load) of the linear propylene polymer portion is 120 g / 10 min or more.
Characteristic (ii): The composition ratio of the linear ethylene / propylene random copolymer portion to the entire linear propylene / ethylene block copolymer (component A) is 2 to 50% by weight.
Characteristics (iii): The intrinsic viscosity _{[eta] copoly} of linear ethylene-propylene random copolymer portion is 5.3~12.0dl / g.
Characteristic (iv): The ethylene content of the linear ethylene / propylene random copolymer portion is 15 to 80% by weight based on the total amount of the linear ethylene / propylene random copolymer.
Characteristic (v): Melt flow rate (230 ° C., 2.16 kg load) is 50 g / 10 min or more.
Characteristic (vi): Ratio (Q value: Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn) is 7-13.
Characteristic (vii): Shows strain hardening in 180 ° C. extensional viscosity measurement. 2. The fibrous filler-containing polypropylene according to claim 1, wherein the propylene-based resin (component A) is composed of the linear propylene / ethylene block copolymer and the other propylene / ethylene block copolymer. Master batch. Furthermore, 40-1000 weight part of talc is contained per 100 weight part of fibrous fillers (component B), The polypropylene type masterbatch of Claim 1 or 2 characterized by the above-mentioned. The fibrous filler-containing polypropylene masterbatch according to any one of claims 1 to 3 , wherein the fatty acid metal salt (component C) is a basic fatty acid metal salt. The resin composition characterized by mixing or kneading the fibrous filler-containing polypropylene masterbatch according to any one of claims 1 to 4 and a polypropylene resin (component D). The fibrous filler-containing polypropylene masterbatch according to any one of claims 1 to 4 , a polypropylene resin (component D) and an elastomer (component E) or / and a non-fibrous filler (component F) are mixed. Or the resin composition characterized by kneading | mixing. The fibrous filler-containing polypropylene masterbatch according to any one of claims 1 to 4 , and a polypropylene resin (component D) and an elastomer (component E) or / and a non-fibrous filler (component F) are mixed in advance. A resin composition obtained by mixing or kneading a kneaded resin composition. 6. The resin composition according to claim 5 , wherein the polypropylene resin (component D) is a propylene / ethylene block copolymer. The resin composition according to claim 6 or 7 , wherein the polypropylene resin (component D) is a propylene / ethylene block copolymer, and the non-fibrous filler (component F) is talc. An injection molding method comprising molding using the resin composition according to any one of claims 5 to 9 . An injection-molded article comprising the resin composition according to any one of claims 5 to 9 .