JP2011195706A - Modifying agent for polypropylene resin, modified polypropylene, use thereof and method for production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modifying agent for polypropylene resin which can enhance impact characteristics of the polypropylene resin with a small addition amount.SOLUTION: The modifying agent (I) for a polypropylene resin has a structure in which a propylene polymer (a1) and an ethylene α-olefin copolymer (b1) are ion-crosslinked by a (meth)acrylate metal salt (c), and is characterized by having a gel fraction of 0.1-90 wt.% by boiled para-xylene extraction.

Description

  The present invention relates to a polypropylene resin modifier and a modified polypropylene resin, their use, and a production method thereof. Specifically, the present invention relates to a polypropylene resin modifier and a modified polypropylene resin capable of improving the mechanical properties of the polypropylene resin, in particular, impact performance, their use, and methods for producing them.

  Polypropylene resin is used in various fields such as daily goods, packaging films, automobile parts, electrical parts, etc., and various modifiers and additives are blended depending on the required performance. Yes.

  For example, in fields requiring high impact performance such as automobile parts, polypropylene resin with improved impact resistance obtained by blending rubber components such as ethylene / α-olefin copolymer rubber with polypropylene resin A composition is used. Among parts that require high impact performance, such as bumpers, it is necessary to increase the compatibility between polypropylene resin and ethylene / α-olefin copolymer rubber and develop impact performance to a higher degree. .

  For example, in Patent Documents 1 to 7, in order to improve the compatibility between polypropylene resin and ethylene / α-olefin copolymer rubber, in addition to ethylene / α-olefin copolymer rubber, propylene / ethylene random copolymer rubber or the rubber A propylene polymer having a rubber part is blended. The propylene / ethylene random copolymer rubber acts as a compatibilizer between the polypropylene resin and the ethylene / α-olefin copolymer rubber. For this reason, when a propylene / ethylene random copolymer rubber is blended with the polypropylene resin composition, the ethylene / α-olefin copolymer rubber is finely dispersed in the polypropylene resin, and higher impact performance is exhibited.

  However, propylene / ethylene random copolymer rubber has a high glass transition temperature. In addition, when a propylene / ethylene random copolymer rubber is blended, there may be an increase in components that are compatible with the polypropylene resin. As a result, the rigidity and impact resistance of the polypropylene resin composition containing the rubber may be reduced with respect to the required characteristics.

Japanese Patent Laid-Open No. 07-126472 JP 2003-147157 A JP 2003-327758 A JP 2006-169424 A JP 2007-284668 A JP 2008-019347 A JP 2009-203257 A

  This invention makes it a subject to provide the modifier for polypropylene resins which can improve the impact performance of a polypropylene resin with a small addition amount. The present invention also provides a polypropylene resin composition excellent in mechanical properties (particularly a balance between rigidity and impact resistance) containing the modifier, a molded article comprising the composition, and production of the modifier. It is also an object to provide a method.

  The present inventors have studied to solve the above problems. As a result, it was found that a polypropylene resin composition excellent in mechanical properties (particularly, balance of rigidity and impact resistance) can be obtained by using the following modifier for polypropylene resin (I), and the present invention was completed. It came to do. That is, the present invention and preferred embodiments thereof relate to the following [1] to [12].

  [1] Propylene polymer (a1) and ethylene / α-olefin copolymer (b1) have at least a structure ion-crosslinked with (meth) acrylic acid metal salt (c), and are obtained by boiling paraxylene extraction. A modifier for polypropylene resin (I) having a gel fraction of 0.1 to 90% by weight.

  [2] Obtained by melt-kneading a propylene polymer (a1), an ethylene / α-olefin copolymer (b1), a (meth) acrylic acid metal salt (c), and an organic peroxide (d). The modifier for polypropylene resin (I) according to [1] above, wherein

  [3] The (meth) acrylic acid metal salt (c) is at least one metal salt selected from zinc (meth) acrylate, magnesium (meth) acrylate, and calcium (meth) acrylate. The modifier for polypropylene resin (I) according to the above [1] or [2].

  [4] The modifier for polypropylene resin (I) according to any one of [1] to [3] above and less than 100 parts by weight and more than 0 parts by weight of the propylene polymer (a2) 99 parts by weight Part or less (provided that the total of component (I) and component (a2) is 100 parts by weight).

  [5] 1 to 20 parts by weight of the modifier for polypropylene resin (I) according to any one of [1] to [3], 98 to 60 parts by weight of a propylene polymer (a2), ethylene / α- A polypropylene resin comprising 1 to 20 parts by weight of an olefin copolymer (b2) (provided that the total of the component (I), the component (a2) and the component (b2) is 100 parts by weight) Composition.

  [6] 1 to 20 parts by weight of the modifier for polypropylene resin (I) according to any one of [1] to [3], 98 to 50 parts by weight of a propylene polymer (a2), and an inorganic filler ( e) 1 to 30 parts by weight (provided that the total of the component (I), the component (a2) and the component (e) is 100 parts by weight).

[7] The polypropylene resin composition according to [6], wherein the inorganic filler (e) is talc.
[8] Propylene polymer (a1) and ethylene / α-olefin copolymer (b1) have at least a structure ion-crosslinked with (meth) acrylic acid metal salt (c), and are obtained by boiling paraxylene extraction. A modified polypropylene resin (I) having a gel fraction of 0.1 to 90% by weight.

[9] A molded article comprising the polypropylene resin composition according to any one of [4] to [7] or the modified polypropylene resin (I) according to [8].
[10] The molded body according to [9], wherein the molded body is an injection molded body, a compression molded body, an injection compression molded body, or an extrusion molded body.

  [11] A step of melt-kneading the propylene polymer (a1), the ethylene / α-olefin copolymer (b1), the (meth) acrylic acid metal salt (c), and the organic peroxide (d). The method for producing a polypropylene resin modifier (I) according to any one of [1] to [3] or the modified polypropylene resin (I) according to [8] above,

  [12] A polymer component comprising 1 to 99 parts by weight of a propylene polymer (a1) and 99 to 1 part by weight of an ethylene / α-olefin copolymer (b1) (provided that the components (a1) and (b1) The total is 100 parts by weight), (meth) acrylic acid metal salt (c) 0.1-5 parts by weight, and organic peroxide (d) 0.01-5 parts by weight The method for producing a polypropylene resin modifier (I) according to any one of [1] to [3] or the modified polypropylene resin (I) according to [8] above,

  ADVANTAGE OF THE INVENTION According to this invention, the modifier for polypropylene resins which can improve the impact performance of a polypropylene resin with a small addition amount can be provided. Also provided are a polypropylene resin composition containing the modifier and excellent in mechanical properties (particularly the balance between rigidity and impact resistance), a molded article composed of the composition, and a method for producing the modifier. You can also

  For example, since the polypropylene resin composition containing the modifier for polypropylene resin (I) of the present invention is excellent in mechanical properties (particularly the balance between rigidity and impact resistance), it is used for medical products and hygiene materials. It is suitably used for various molded products and various thin-walled molded products such as products, packaging products, food containers, food packaging, automotive products, electronic material products, OA equipment housing parts, building material parts, and home appliances.

  Hereinafter, the present invention will be specifically described. In the present invention, “propylene polymer” and “polypropylene resin” are sometimes used interchangeably. In addition, the content of the structural unit derived from the monomer may be simply referred to as “monomer content”.

[Modified polypropylene resin (I) / Modifier for polypropylene resin (I)]
The modified polypropylene resin (I) of the present invention is formed from a propylene polymer (a1) (polypropylene resin (a1)), an ethylene / α-olefin copolymer (b1), and a (meth) acrylic acid metal salt (c). Preferably, the propylene polymer (a1) and the ethylene / α-olefin copolymer (b1) have at least a structure in which the (meth) acrylic acid metal salt (c) is ionically crosslinked.

  The modified polypropylene resin (I) of the present invention has a gel fraction by boiling paraxylene extraction of 0.1 to 90% by weight, preferably 0.1 to 80% by weight. When the gel fraction by boiling paraxylene extraction is outside the above range, high impact performance may not be exhibited. In addition, the measuring method of a gel fraction is as having described in the Example.

  The melt flow rate (MFR, ASTM D1238, 230 ° C., 2.16 kg load) of the modified polypropylene resin (I) of the present invention is usually 0.05 to 200 g / 10 minutes, preferably 0.1 to 150 g / 10 minutes. is there.

  The modified polypropylene resin (I) of the present invention includes, for example, a propylene polymer (a1), an ethylene / α-olefin copolymer (b1), a (meth) acrylic acid metal salt (c), and an organic peroxide. It is obtained by melt-kneading (d). Details of the method for producing the resin (I) will be described later.

  Since the modified polypropylene resin (I) of the present invention has excellent mechanical properties, it can be suitably used as a constituent resin of a molded body. Moreover, since the modified polypropylene resin (I) of the present invention has excellent properties as a modifier for polypropylene resins, it can be suitably used as a modifier for polypropylene resins.

  In the following description, when the modified polypropylene resin (I) is used as a modifier for polypropylene resin, it may be described as “polypropylene resin modifier (I)”. Hereinafter, the case where the modified polypropylene resin (I) is used as a modifier of the polypropylene resin will be mainly described, but the physical properties and the like are the same in other cases.

  By blending the polypropylene resin modifier (I) of the present invention with a polypropylene resin, the mechanical properties (eg, impact performance such as high-speed impact strength) of the resulting polypropylene resin composition can be greatly improved. . About this reason, the present inventors guess as follows.

It is usually difficult to finely disperse the ethylene / α-olefin copolymer (b1) alone in the polypropylene resin to be added. However,
(I) The propylene polymer (a1) and the ethylene / α-olefin copolymer (b1) constituting the modifier for polypropylene resin (I) of the present invention are passed through a (meth) acrylic acid metal salt (c). In this case, the interaction between the component derived from (a1) and the component derived from (b1) is moderately strengthened.
(Ii) When the above modifier (I) and the polypropylene resin to be added are melt-kneaded, the component derived from (a1) and the component derived from (b1) are maintained in an appropriately interacting state. However, the ionic crosslinking (ionic bond) is loosened moderately,
it is conceivable that.

  Therefore, even if the gel fraction of the modifier (I) itself is high, the component derived from (b1) can be finely dispersed in the polypropylene resin to be added by melt kneading, and a small amount of ( b1) It is presumed that high impact performance is manifested by the amount of component added.

On the other hand, a crosslinked product obtained by melt-kneading a propylene polymer, an ethylene / α-olefin copolymer, an organic peroxide, and a compound having two or more unsaturated bonds (eg, divinylbenzene), It has not a structure crosslinked by ionic bonds but a structure firmly crosslinked by covalent bonds. Therefore, when the gel fraction of the crosslinked product is high, the component derived from the ethylene / α-olefin copolymer is finely dispersed in the polypropylene resin even if the crosslinked product and the polypropylene resin to be added are melt-kneaded. Without high impact performance.
Hereinafter, each component that can be used in the present invention will be described.

Propylene polymer (a1)
Examples of the propylene polymer (a1) include a propylene homopolymer and a copolymer mainly composed of propylene. A propylene polymer (a1) may be used individually by 1 type, and may use 2 or more types together.

  Here, the “propylene-based” copolymer means that the content of the propylene-derived structural unit in the copolymer is 85 mol% or more and less than 100 mol%. Examples of structural units other than propylene include structural units derived from α-olefins other than propylene. Specific examples of the copolymer include a propylene / α-olefin random copolymer and a propylene / α-olefin block copolymer, and a propylene / α-olefin random copolymer is preferable.

  Examples of the α-olefin include α-olefins having 2 to 12 carbon atoms (excluding propylene). Specifically, ethylene, 1-butene, 2-methyl-1-propene, 2-methyl- 1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1 -Butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pente , Propyl-1-pentene, 1-nonene, 1-decene, 1-undecene, 1-dodecene and the like. Of these, ethylene is preferred. The said alpha olefin may be used individually by 1 type, and may use 2 or more types together.

  The melt flow rate (MFR, ASTM D1238, 230 ° C., 2.16 kg load) of the propylene polymer (a1) is usually 0.5 to 500 g / 10 minutes, preferably 5 to 300 g / 10 minutes. If the MFR is too small, the melt fluidity of the resulting polypropylene resin modifier (I) may be inferior. If the MFR is excessive, the mechanical strength of the resulting polypropylene resin modifier (I) may be inferior.

  The propylene polymer (a1) can be produced by a known polymerization method using a known olefin polymerization catalyst. Examples of the olefin polymerization catalyst include Ziegler-Natta catalysts, complex catalysts such as metallocene complexes and nonmetallocene complexes. Examples of the polymerization method include a slurry polymerization method, a solution polymerization method, a bulk polymerization method, and a gas phase polymerization method. Moreover, as a propylene polymer (a1), it is also possible to use a commercially available product.

Ethylene / α-olefin copolymer (b1)
The type of the ethylene / α-olefin copolymer (b1) is not particularly limited. The ethylene / α-olefin copolymer (b1) may be used alone or in combination of two or more.

  The ethylene / α-olefin copolymer (b1) is an ethylene / α-olefin copolymer rubber having an ethylene content of 20 to 95 mol% and an α-olefin content of 3 to 20 carbon atoms of 80 to 5 mol%. Preferably, an ethylene / α-olefin copolymer rubber having an ethylene content of 30 to 90 mol% and an α-olefin content of 3 to 20 carbon atoms of 70 to 10 mol% is more preferable. However, the total of the ethylene content and the C3-C20 α-olefin content is 100 mol%.

  Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene and 1-dodecene. 1-tetradecene, 1-hexadecene, 1-eicosene and the like. In these, C3-C12 alpha olefins, such as propylene, 1-butene, 1-hexene, 1-octene, are preferable. The said C3-C20 alpha olefin may be used individually by 1 type, and may use 2 or more types together.

  The melt flow rate (MFR, ASTM D1238, 230 ° C., 2.16 kg load) of the ethylene / α-olefin copolymer (b1) is usually 0.5 to 100 g / 10 minutes, preferably 1 to 70 g / 10 minutes. is there. If the MFR is too small, the melt fluidity of the resulting polypropylene resin modifier (I) may be inferior. If the MFR is excessive, the mechanical strength of the resulting polypropylene resin modifier (I) may be inferior.

  The ethylene / α-olefin copolymer (b1) can be produced by a known polymerization method using a known catalyst for olefin polymerization as a copolymerization of ethylene and the α-olefin having 3 to 20 carbon atoms. Examples of the olefin polymerization catalyst include Ziegler-Natta catalysts, complex catalysts such as metallocene complexes and nonmetallocene complexes. Examples of the polymerization method include a slurry polymerization method, a solution polymerization method, a bulk polymerization method, and a gas phase polymerization method. As the ethylene / α-olefin copolymer (b1), a commercially available product can also be used.

(Meth) acrylic acid metal salt (c)
The (meth) acrylic acid metal salt (c) is a metal salt obtained by neutralizing the carboxyl group of (meth) acrylic acid with a metal. In the present invention, (meth) acrylic acid means one or more selected from acrylic acid and methacrylic acid.

  As (meth) acrylic acid metal salt (c), sodium acrylate, potassium acrylate, calcium acrylate, magnesium acrylate, zinc acrylate, aluminum acrylate, sodium methacrylate, potassium methacrylate, calcium methacrylate, methacryl Examples thereof include magnesium acid, zinc methacrylate, and aluminum methacrylate. Among these, zinc acrylate, magnesium acrylate, calcium acrylate, zinc methacrylate, magnesium methacrylate, and calcium methacrylate neutralized with a divalent metal are preferred; zinc methacrylate, magnesium methacrylate, methacryl Calcium acid is particularly preferred. The (meth) acrylic acid metal salt (c) may be used alone or in combination of two or more.

  The structural unit derived from the (meth) acrylic acid metal salt (c) is usually in the range of 0.1 to 5% by weight, preferably 0.1 to 2% by weight in the polypropylene resin modifier (I) of the present invention. Included. When the content of the structural unit is out of the above range, high impact performance may not be exhibited.

Organic peroxide (d)
As the organic peroxide (d), a known organic peroxide can be used without limitation.
Specifically, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butyl) Peroxyketals such as peroxy) octane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane;
Di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, α, α'-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t- Dialkyl peroxides such as butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3;
Acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,5-dichlorobenzoyl peroxide, m-tri Diacyl peroxides such as oil peroxide;
t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, di-t-butylper Peroxyesters such as oxyisophthalate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropylcarbonate, cumylperoxyoctate ;
Peroxydicarbonates such as di (2-ethylhexyl) peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate;
such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, etc. Hydroperoxides;
Di (3-methyl-methoxybutyl) peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarb Bonates, di-2-ethylhexyl peroxydicarbonate, di-n-butyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxycarbonate, dicetyl peroxydicarbonate Examples thereof include oxydicarbonates.

  Among these, benzoyl peroxide, m-trioyl peroxide, t-butylperoxy-2-ethylhexanoate, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxide Oxy) hexane, t-butyl peroxybenzoate, dicetyl peroxydicarbonate and the like are preferable.

  An organic peroxide (d) may be used individually by 1 type, and may use 2 or more types together. In order to improve the handling of the organic peroxide (d), a master batch of the organic peroxide (d) in which an inert compound such as a resin or silica is blended as a binder may be used.

[Modified Polypropylene Resin (I) / Production Method for Polypropylene Resin Modifier (I)]
The production method of the modified polypropylene resin (I) (or the modifier for polypropylene resin (I)) of the present invention is not particularly limited, but preferred production methods include propylene polymer (a1), ethylene / α -The method of melt-kneading olefin copolymer (b1), (meth) acrylic acid metal salt (c), and organic peroxide (d) is mentioned.

  More specifically, the method for producing the modified polypropylene resin (I) (or the modifier for polypropylene resin (I)) of the present invention comprises 1 to 99 parts by weight of the propylene polymer (a1) and ethylene / α-olefin. Polymer component (b1) consisting of 99 to 1 part by weight (provided that the total of component (a1) and component (b1) is 100 parts by weight) and (meth) acrylic acid metal salt (c) 0 It is preferable to have a step of melt-kneading 0.1 to 5 parts by weight and 0.01 to 5 parts by weight of the organic peroxide (d). Thus, it is preferable to melt-modify the mixture of the component (a1) and the component (b1).

  The proportion of the propylene polymer (a1) in the polymer component is usually 1 to 99 parts by weight, preferably 10 to 90 parts by weight, more preferably 30 to 70 parts by weight; an ethylene / α-olefin copolymer. The proportion of (b1) is usually 99 to 1 part by weight, preferably 90 to 10 parts by weight, more preferably 70 to 30 parts by weight. However, the sum total of the component (a1) and the component (b1) is 100 parts by weight. When the use ratio of these components is in the above range, it is preferable from the viewpoint of impact resistance. The polymer component may contain a polymer other than the component (a1) and the component (b1).

  The amount of the (meth) acrylic acid metal salt (c) used is usually 0.1 to 5 parts by weight, preferably 0.1 to 2 parts per 100 parts by weight in total of the components (a1) and (b1). Part by weight, more preferably 0.2 to 1 part by weight. (C) It is preferable from a viewpoint of impact resistance expression that the usage rate of a component exists in the said range.

  The amount of the organic peroxide (d) used is usually 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the total of the components (a1) and (b1). More preferably, it is 0.1 to 1 part by weight. (D) It is preferable from a viewpoint of impact resistance expression that the usage rate of a component exists in the said range.

  As a melt modification method used as a method for producing the modifier for polypropylene resin (I), a known method for mixing resins or a resin and a solid or liquid additive can be employed. Preferable examples include mixing all of the above components, or combining a part of each of the above components and mixing them separately, further mixing to form a uniform mixture, and then kneading the mixture. A method can be mentioned.

  Conventionally known forming means can be widely used as the mixture forming means, and examples thereof include a Henschel mixer, a ribbon blender, and a blender. As the kneading means for the mixture, conventionally known kneading means can be widely adopted, and examples thereof include a Banbury mixer, a plast mill, a Brabender plastograph, a single screw or a twin screw extruder, and among these, a twin screw extrusion It is preferable to employ a machine. Moreover, when it is desired to remove ungrafted components such as the (meth) acrylic acid metal salt (c), a kneader having a vacuum vent device may be used.

  The temperature at the time of kneading in a kneader (for example, cylinder temperature in the case of an extruder) is usually 100 to 300 ° C, preferably 120 to 250 ° C. If the temperature is too low, the ionic crosslinking reaction with the (meth) acrylic acid metal salt (c) may not proceed. If the temperature is too high, decomposition of the resin (polymer) may occur.

[Polypropylene resin composition]
The polypropylene resin composition of the present invention contains a modifier for polypropylene resin (I) and a propylene polymer (a2) (polypropylene resin (a2)). In addition, the polypropylene resin composition of the present invention may contain an ethylene / α-olefin copolymer (b2), an inorganic filler (e), various additives, and the like.

  By using the polypropylene resin composition of the present invention containing the above-mentioned modifier for polypropylene resin (I), the balance of rigidity, impact resistance, heat resistance and hardness is excellent, for example, with excellent mechanical properties. A molded product can be obtained.

Propylene polymer (a2)
As a propylene polymer (a2), the polymer illustrated as a propylene polymer (a1) used at the time of formation of the modifier (I) for polypropylene resins mentioned above is mentioned. Further, as the propylene polymer (a2), the same polymer as the propylene polymer (a1) used at the time of forming the above-described modifier (I) for polypropylene resin may be used, or a different polymer may be used. May be.

In the polypropylene resin composition of the present invention, the content of the modifier for polypropylene resin (I) is usually 1 part by weight or more and less than 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 1 to 40 parts by weight. Yes; The content of the propylene polymer (a2) is usually more than 0 parts by weight and 99 parts by weight or less, preferably 50 to 99 parts by weight, more preferably 60 to 99 parts by weight. However, the total of the modifier for polypropylene resin (I) and the propylene polymer (a2) is 100 parts by weight. The content of each component may be the blending amount of each component during the production of the polypropylene resin composition.
When the content of the propylene polymer (a2) is within the above range, not only high impact performance can be exhibited, but also rigidity, heat resistance, mechanical properties (eg, hardness) and the like can be improved.

Ethylene / α-olefin copolymer (b2)
The polypropylene resin composition of the present invention may further contain an ethylene / α-olefin copolymer (b2). Examples of the ethylene / α-olefin copolymer (b2) of the present invention include those similar to the ethylene / α-olefin copolymer (b1) used during the formation of the above-described polypropylene resin modifier (I). . As the ethylene / α-olefin copolymer (b2), the same one as the ethylene / α-olefin copolymer (b1) used during the formation of the modifier for polypropylene resin (I) described above may be used. However, different ones may be used.

  When the ethylene / α-olefin copolymer (b2) is used, the content of the modifier (I) for polypropylene resin is usually 1 to 20 parts by weight, preferably 5 to 20 parts by weight; The content of a2) is usually 98 to 60 parts by weight, preferably 90 to 60 parts by weight; the content of the ethylene / α-olefin copolymer (b2) is usually 1 to 20 parts by weight, preferably 5 ~ 20 parts by weight. However, the total of the modifier for polypropylene resin (I), the propylene polymer (a2), and the ethylene / α-olefin copolymer (b2) is 100 parts by weight. The content of each component may be the blending amount of each component during the production of the polypropylene resin composition.

  When the content of the ethylene / α-olefin copolymer (b2) is within the above range, the polypropylene resin modifier (I) acts as a compatibilizing agent for the ethylene / α-olefin copolymer (b2). Therefore, it is possible to obtain a polypropylene resin composition superior in rigidity and impact resistance.

Inorganic filler (e)
The polypropylene resin composition of the present invention may further contain an inorganic filler (e). The inorganic filler (e) can be used, for example, to improve the bending elastic modulus of the molded body.

  The composition, shape, etc. of the inorganic filler (e) are not particularly limited, and any of those commercially available as polymer fillers can be used. As the inorganic filler (e), plate-like inorganic fillers such as talc, mica and montmorillonite; fibrous inorganic fillers such as glass fiber, carbon fiber and aramid fiber; potassium titanate, basic magnesium sulfate, wollastonite And needle-like (whisker) inorganic fillers. Among these, talc is particularly preferable from the viewpoint of physical properties and cost. Furthermore, talc having an average particle diameter measured by a laser diffraction method of 1 to 10 μm is preferable, and talc having 1 to 5 μm is more preferable.

  When the inorganic filler (e) is used, the content of the modifier (I) for polypropylene resin is usually 1 to 20 parts by weight, preferably 1 to 10 parts by weight; content of the propylene polymer (a2) Is usually 98-50 parts by weight, preferably 94-60 parts by weight; the content of the inorganic filler (e) is usually 1-30 parts by weight, preferably 5-20 parts by weight. However, the total of the modifier for polypropylene resin (I), the propylene polymer (a2) and the inorganic filler (e) is 100 parts by weight. The content of each component may be the blending amount of each component during the production of the polypropylene resin composition.

  When the content of the inorganic filler (e) is within the above range, it is possible to obtain a polypropylene resin composition having excellent light weight and heat resistance while maintaining the mechanical properties of the polypropylene resin composition. it can.

Various Additives The polypropylene resin composition of the present invention may contain various additives as necessary. As said additive, if it is generally used as an additive for resin, it can be used without a restriction | limiting in particular. Specific examples of the additive include an antioxidant, an ultraviolet absorber, an antistatic agent, a nucleating agent, a lubricant, a flame retardant, a heat stabilizer, an antiblocking agent, a colorant, and various synthetic resins. Can be mentioned.

[Production method of polypropylene resin composition]
The polypropylene resin composition of the present invention can be produced, for example, by kneading the above components in the above proportions at a preset temperature of 180 to 250 ° C. using a conventionally known kneader. Examples of the kneader include an extruder, a Banbury mixer, and a kneader. An extruder is preferable, and a twin-screw extruder is particularly preferable. Moreover, you may mix said each component in the said ratio using a tumbler mixer etc. before the said kneading | mixing.

[Molded body]
The molded product of the present invention is composed of the polypropylene resin composition or modified polypropylene resin (I) of the present invention. Here, when the modified polypropylene resin (I) is used as the constituent resin of the molded body, a component other than the propylene polymer (a2) in the polypropylene resin composition may be used together with the resin (I).

  The molded body of the present invention is produced, for example, by melt-kneading the polypropylene resin composition or modified polypropylene resin (I) of the present invention, followed by pelletizing, and molding the obtained pellets using various molding methods. be able to.

  For melt kneading of the polypropylene resin composition or modified polypropylene resin (I) of the present invention, conventionally known kneaders such as a Henschel mixer, a ribbon blender, and a Banbury mixer can be used. For melt-kneading and pelletizing, conventionally known single-screw or twin-screw extruders, Brabenders or rolls can be used. The melt-kneading and pelletizing are usually performed at 170 to 300 ° C, preferably 190 to 250 ° C.

  Examples of the molding method include injection molding, extrusion molding, and hollow molding. Examples of the molded body thus obtained include injection molded bodies, compression molded bodies, injection compression molded bodies, extrusion molded bodies, and hollow molded bodies.

  The molded product obtained from the polypropylene resin composition or modified polypropylene resin (I) of the present invention is excellent in the balance of rigidity, impact resistance, heat resistance and hardness, so that it is a medical product, hygiene product, packaging product. It is suitably used for various molded articles and various thin-walled molded articles such as food containers, food packaging, automobile products, electronic material products, OA equipment housing parts, building material parts, and home appliances.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following examples, comparative examples, and reference examples, each property of the polypropylene resin composition and its components was measured as follows.

(* 1) Melt flow rate (MFR)
MFR was measured at 230 ° C. and a load of 2.16 kg according to ASTM D1238.
(* 2) Gel fraction The gel fraction is calculated from the following formula based on the charged amount and the remaining amount in the wire mesh by charging about 2g of the sample into a # 400 mesh wire mesh and extracting with boiling paraxylene reflux for 6 hours. Calculated by
Gel fraction (%) = (residual amount [g] / charge amount [g]) × 100
(* 3) Tensile elongation Tensile elongation was measured under the following conditions in accordance with JIS K7162-1BA.

<Measurement conditions>
-Test piece: JIS K7162-1BA dumbbell
5mm (width) x 2mm (thickness) x 75mm (length)
・ Tensile speed: 20 mm / min ・ Span distance: 58 mm
(* 4) Flexural modulus The flexural modulus (FM) was measured under the following conditions in accordance with JIS K7171.

<Measurement conditions>
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
・ Bending speed: 2 mm / min ・ Bending span: 64 mm
(* 5) Charpy impact strength Charpy impact strength was measured under the following conditions in accordance with JIS K7111.

<Measurement conditions>
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length) (cutting notch)
・ Measurement temperature: 23 ℃
(* 6) Load deflection temperature (heating deformation temperature)
The load deflection temperature was measured under the following conditions in accordance with JIS K7191.

<Measurement conditions>
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
(* 7) Surface hardness (Rockwell hardness)
The surface hardness was measured in accordance with JIS K7202 (R-scale) using two 2 mm thick square plates.
(* 8) High-speed surface impact strength The total fracture energy was measured under the following conditions to obtain the high-speed surface impact strength.

<Test conditions>
・ Temperature: -30 ℃
Test piece: 3 mm (width) x 3 mm (length) x 2 mm (thickness) (square plate)
・ Speed: 3m / s
・ Shock core: 1/2 inch φ
・ Receiver: 1 inch φ

<Raw material>
(1) Propylene polymer (a1)
(A1-1): F228P manufactured by Prime Polymer Co., Ltd. (propylene / ethylene random copolymer, propylene content = 96 mol%, MFR = 10 g / 10 min)
(A1-2): J105G manufactured by Prime Polymer Co., Ltd.
(Propylene homopolymer, MFR = 10 g / 10 min)
(A1-3): Prime Polymer Co., Ltd. J13B
(Propylene homopolymer, MFR = 200 g / 10 min)

(2) Ethylene / α-olefin copolymer (b1)
(B1-1): Mitsui Chemicals Toughmer A4050S (ethylene-butene copolymer, ethylene content = 80 mol%, MFR = 6.5 g / 10 min)
(B1-2): ENGAGE8200 (ethylene / 1-octene copolymer, ethylene content = 90 mol%, MFR = 10 g / 10 min) manufactured by DuPont Dow Elastomer Co., Ltd.
(B1-3): Tuffmer A35070S manufactured by Mitsui Chemicals, Inc. (ethylene / butene copolymer, ethylene content = 85 mol%, MFR = 65 g / 10 min)
(B1-4): Tuffmer A0550S manufactured by Mitsui Chemicals, Inc. (ethylene / butene copolymer, ethylene content = 80 mol%, MFR = 1 g / 10 min)

(3) Propylene polymer (a2)
(A2-1): J13B manufactured by Prime Polymer Co., Ltd.
(Propylene homopolymer, MFR = 200 g / 10 min)
(A2-2): J-3000GV manufactured by Prime Polymer Co., Ltd.
(Propylene homopolymer, MFR = 30 g / 10 min)
(A2-3): J707G manufactured by Prime Polymer Co., Ltd.
(Propylene / ethylene block copolymer, MFR = 30 g / 10 min)

(4) Ethylene / α-olefin copolymer (b2)
(B2-1): Mitsui Chemicals Toughmer A4050S (ethylene-butene copolymer, ethylene content = 80 mol%, MFR = 6.5 g / 10 min)
(B2-2): ENGAGE 8200 (ethylene / 1-octene copolymer, ethylene content = 90 mol%, MFR = 10 g / 10 min) manufactured by DuPont Dow Elastomer Co., Ltd.
(B2-3): Tuffmer A0550S manufactured by Mitsui Chemicals, Inc. (ethylene / butene copolymer, ethylene content = 80 mol%, MFR = 1 g / 10 min)

Preparation of modifier (I) for polypropylene resin [Example 1]
(A1) 30 parts by weight as component (a1-1), 70 parts by weight (b1-1) as component (b1), and zinc methacrylate as component (c) (R-20S manufactured by Asada Chemical Co., Ltd.) 1 part by weight and 0.5 part by weight of t-butyl peroxybenzoate (Nippon Yushi Co., Ltd., Perbutyl Z.) as a component (d) are uniformly mixed with a Henschel mixer, and then the same-direction twin-screw kneader Heat-kneading was carried out at 210 ° C. (KZW31-30HG manufactured by Technobel Co., Ltd.) to obtain a polypropylene resin modifier (I-1). Table 1 shows the properties of the resulting modifier for polypropylene resin.

[Examples 2 to 9]
In Example 1, the modifiers (I-2) to (I-9) for polypropylene resin were obtained in the same manner as in Example 1 except that the components in the amounts shown in Table 1 were used. Table 1 shows the properties of the resulting modifier for polypropylene resin.

[Reference Example 1]
In Example 1, a crosslinked ethylene / butene copolymer was prepared in the same manner as in Example 1 except that 100 parts by weight of (b1-1) component was used without using (a1) component. (I-1) was obtained. Table 1 shows the properties of the obtained crosslinked product.

[Reference Example 2]
In Example 1, instead of component (c), cross-linking of a propylene polymer and an ethylene / butene copolymer was performed in the same manner as in Example 1 except that 1 part by weight of bismaleimide (Matrimid 5292A manufactured by Ciba) was used. The body (i-2) was obtained. Table 1 shows the properties of the obtained crosslinked product.

[Reference Example 3]
In Example 1, instead of the component (c), a propylene polymer and ethylene / ethylene acrylate were used in the same manner as in Example 1 except that 1 part by weight of pentaerythritol triacrylate (V # 300, manufactured by Osaka Organic Chemical Industry) was used. A cross-linked product (i-3) with a butene copolymer was obtained. Table 1 shows the properties of the obtained crosslinked product.

Preparation of polypropylene resin composition [Example 10]
The polypropylene resin modifier (I-5) obtained in Example 5 was directly injection molded by an injection molding machine (EC40NII manufactured by Toshiba Machine Co., Ltd.) under the conditions of a heating temperature of 190 ° C. and a cooling temperature of 40 ° C. A test piece was prepared and its properties were measured. The results are shown in Table 2.

[Example 11]
Tumble mixer with 39.5 parts by weight of (a2-1) and 39.5 parts by weight of (a2-2) as component (a2) and 21 parts by weight of (I-4) obtained in Example 4 as component (I) And then uniformly kneaded at 190 ° C. with a biaxial kneader (KZW-15T manufactured by Technobel Co., Ltd.) to obtain a polypropylene resin composition. The obtained polypropylene resin composition was injection-molded by the method described in Example 10, a test piece was produced, and its properties were measured. The results are shown in Table 2.

[Examples 12 to 15]
In Example 11, a polypropylene resin composition and a test piece were obtained in the same manner as in Example 11 except that the components in the amounts shown in Table 2 were used as the component (a2) and the component (I). The results are shown in Table 2.

[Comparative Examples 1-3]
In Example 11, the component of the amount described in Table 2 was used as the component (a2), and the component of the amount described in Table 2 was used as the component (b2) instead of the component (I). In the same manner as above, a polypropylene resin composition and a test piece were obtained. The results are shown in Table 2.

[Examples 16 to 19]
In Example 11, a polypropylene resin composition and a test piece were obtained in the same manner as in Example 11 except that the components shown in Table 3 were used as the component (a2) and the component (I). The results are shown in Table 3.

[Example 20]
In Example 11, the components described in Table 3 were used as the components (a2) and (I), and the components described in Table 3 were used as the component (b2). Similarly, a polypropylene resin composition and a test piece were obtained. The results are shown in Table 3.

[Comparative Examples 4 to 6]
In Example 11, the component of the amount described in Table 3 was used as the component (a2), and the component of the amount described in Table 3 was used as the component (b2) instead of the component (I). In the same manner as above, a polypropylene resin composition and a test piece were obtained. The results are shown in Table 3.

[Comparative Examples 7 to 9]
In Example 11, the component described in Table 3 was used as the component (a2), and the component described in Table 3 was used as the component (i) (crosslinked product) obtained in Reference Example instead of the component (I). A polypropylene resin composition and a test piece were obtained in the same manner as in Example 11 except that the components were used. The results are shown in Table 3.

  The modifiers (i-2) and (i-3) of Reference Examples 2 and 3 have a structure in which the component (a1-1) and the component (b1-1) are firmly cross-linked by a covalent bond. When the gel fraction of the crosslinked product is as large as the modifier (see Table 1), the crosslinked product is not dispersed in the polypropylene resin. For this reason, when the said modifier (crosslinked body) is added to a polypropylene resin, impact performance will fall (refer Example 16 and Comparative Examples 8 and 9).

  However, the gel fraction of the modifier (I-1) of Example 1 is much larger than the gel fractions of the modifiers (i-2) and (i-3) of Reference Examples 2 and 3. Nevertheless (see Table 1), the polypropylene resin composition obtained by adding the modifier (I-1) of Example 1 exhibits a high impact performance (see Example 16).

  In the modifier (I) obtained in the examples, the component derived from (a1) and the component derived from (b1) interact through ionic crosslinking (ionic bond), and the polypropylene resin While maintaining the state in which the component derived from (a1) and the component derived from (b1) interacted moderately at the time of melt kneading, the component derived from (b1) Is presumed to be finely dispersed in the polypropylene resin.

  Therefore, in the polypropylene resin modifier (I) of the present invention, the propylene polymer (a1) and the ethylene / α-olefin copolymer (b1) are ion-crosslinked by the (meth) acrylic acid metal salt (c). It was concluded that it has at least the structure.

[Examples 21 to 24]
In Example 11, the components described in Table 4 were used as the component (a2) and the component (I), and the amount of talc described in Table 4 as the component (e) (JM-209 manufactured by Asada Flour Milling Co., Ltd.). A polypropylene resin composition and a test piece were obtained in the same manner as in Example 11 except that an average particle diameter of about 4 μm determined by a laser diffraction method was used. The results are shown in Table 4.

[Comparative Examples 10-12]
In Example 11, the component described in Table 4 was used as the component (a2), and the component described in Table 4 was used as the component (i) (crosslinked product) obtained in Reference Example instead of the component (I). Example 11 except that the components were used and the amount of talc described in Table 4 was used as component (e) (JM-209 manufactured by Asada Flour Milling Co., Ltd., average particle diameter of about 4 μm determined by laser diffraction method). In the same manner as above, a polypropylene resin composition and a test piece were obtained. The results are shown in Table 4.

  By blending the polypropylene resin modifier (I) of the present invention into a polypropylene resin, a polypropylene resin composition having an excellent balance of rigidity, impact resistance, heat resistance and hardness can be obtained. The polypropylene resin composition thus obtained can be used for medical products, hygiene products, packaging products, food containers, food packaging, automotive products, electronic material products, and OA equipment. It can be suitably used for various molded products and various thin molded products such as housing parts, building material parts, and home appliances.

Claims (12)

Propylene polymer (a1) and ethylene / α-olefin copolymer (b1) have at least a structure ion-crosslinked with (meth) acrylic acid metal salt (c), and gel fraction by boiling paraxylene extraction Is a modifier for polypropylene resin (I), characterized by comprising 0.1 to 90% by weight.   It is obtained by melt-kneading a propylene polymer (a1), an ethylene / α-olefin copolymer (b1), a (meth) acrylic acid metal salt (c), and an organic peroxide (d). The modifier (I) for polypropylene resin according to claim 1, which is characterized by the following.   The (meth) acrylic acid metal salt (c) is one or more metal salts selected from zinc (meth) acrylate, magnesium (meth) acrylate, and calcium (meth) acrylate. Item 3. The modifier for polypropylene resin (I) according to item 1 or 2.   It contains 1 part by weight or more and less than 100 parts by weight of the modifier for polypropylene resin (I) according to any one of claims 1 to 3, and more than 0 part by weight of the propylene polymer (a2) and 99 parts by weight or less. (However, the sum total of (I) component and (a2) component is 100 weight part). The polypropylene resin composition characterized by the above-mentioned. 1 to 20 parts by weight of the modifier for polypropylene resin (I) according to any one of claims 1 to 3,
98-60 parts by weight of propylene polymer (a2);
1 to 20 parts by weight of the ethylene / α-olefin copolymer (b2) (provided that the total of the component (I), the component (a2) and the component (b2) is 100 parts by weight) A polypropylene resin composition. 1 to 20 parts by weight of the modifier for polypropylene resin (I) according to any one of claims 1 to 3,
98-50 parts by weight of propylene polymer (a2);
A polypropylene resin composition comprising 1 to 30 parts by weight of an inorganic filler (e) (provided that the total of component (I), (a2) and (e) is 100 parts by weight) object.   The polypropylene resin composition according to claim 6, wherein the inorganic filler (e) is talc. Propylene polymer (a1) and ethylene / α-olefin copolymer (b1) have at least a structure ion-crosslinked with (meth) acrylic acid metal salt (c), and gel fraction by boiling paraxylene extraction Is a modified polypropylene resin (I), characterized in that it is 0.1 to 90% by weight.   A molded product comprising the polypropylene resin composition according to any one of claims 4 to 7 or the modified polypropylene resin (I) according to claim 8.   The molded body according to claim 9, wherein the molded body is an injection molded body, a compression molded body, an injection compression molded body, or an extrusion molded body.   Having a step of melt-kneading the propylene polymer (a1), the ethylene / α-olefin copolymer (b1), the (meth) acrylic acid metal salt (c), and the organic peroxide (d). The method for producing a modifier for polypropylene resin (I) according to any one of claims 1 to 3, or a modified polypropylene resin (I) according to claim 8, characterized in that it is characterized in that Polymer component consisting of 1 to 99 parts by weight of propylene polymer (a1) and 99 to 1 part by weight of ethylene / α-olefin copolymer (b1) (provided that the total of component (a1) and component (b1) is 100 Parts by weight)
(Meth) acrylic acid metal salt (c) 0.1-5 parts by weight;
The modifier (I) for polypropylene resin according to any one of claims 1 to 3, further comprising a step of melt kneading 0.01 to 5 parts by weight of the organic peroxide (d). Item 9. A method for producing the modified polypropylene resin (I) according to Item 8.