Auxiliary agent for filler-reinforced resin, filler-reinforced resin composition, molded article thereof, and method for producing filler-reinforced resin composition

Abstract

To provide an auxiliary agent for filler-reinforced resin that allows a molded article having excellent mechanical properties, such as impact resistance and bending strength, to be obtained, and to provide a filler-reinforced resin composition containing the auxiliary agent and the molded article thereof.SOLUTION: An auxiliary agent for filler-reinforced resin satisfies the following requirements (i) and (ii): (i) it contains a graft-modified product in which at least one kind of base polymer selected from polyolefins is graft-modified with a carbodiimide monomer represented by the following formula (1) or another specific structure; and (ii) it contains carbodiimide groups in an amount of 0.1 to 50 mmol per 100 g of the auxiliary agent for filler-reinforced resin.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an auxiliary agent for filler-reinforced resin, a filler-reinforced resin composition, a molded article thereof, and a method for producing the filler-reinforced resin composition.

Background Art

[0002] Polyolefins such as polypropylene and polyethylene are molded by various methods and are used in a wide range of applications. However, polyolefins, particularly polypropylene, may not have sufficient heat resistance, rigidity, and strength depending on the application. In such cases, they are reinforced using fillers such as talc, glass fiber, and carbon fiber. However, in a filler-reinforced resin composition containing polypropylene and a filler, the dispersion of the filler is often insufficient, or the adhesion between polypropylene and the filler is low, resulting in many cases where the reinforcing effect of the filler is not sufficient. For this reason, when melt-compounding polypropylene and a filler, in order to improve the adhesion between polypropylene and the filler, various silane coupling agents or titanate-based coupling agents are added, or the surface of the filler is treated with a higher fatty acid or the like, but the effect is not sufficient.

[0003] Particularly when an inorganic filler such as glass fiber is used as the filler, as reported in Patent Document 1, it is known that the mechanical properties of the composition can be improved by adding maleic anhydride-modified polypropylene or the like to improve the adhesion between polypropylene and the filler.

[0004] In addition, attempts have been made to further disperse carbon fibers to improve the reinforcing effect. For example, Patent Document 2 discloses a carbon fiber resin composition in which carbon fibers treated with a sizing agent are treated with maleic anhydride-modified polypropylene. However, although the maleic anhydride-modified polypropylene has improved impregnation properties with respect to carbon fibers compared to untreated polypropylene, the strength of the molded body formed from the composition has remained insufficient. As a countermeasure, attempts have been made to use a composition containing an olefin resin modified with an amino group or an epoxy group instead of the maleic anhydride-modified polypropylene (for example, Patent Document 3), but the practical strength of the molded body formed from the composition is still insufficient.

[0005] On the other hand, Patent Document 4 uses a reaction product of a polar group-containing polyolefin and a carbodiimide group-containing compound as a compatibilizer for a polar group-containing polymer and an olefin polymer. However, the compatibilizer relates to compatibilization between polymer molecules and does not disclose anything regarding improving the strength of a filler-reinforced olefin. In addition, Patent Document 5 discloses an adhesive containing a carbodiimide group-modified olefin. However, although Patent Document 5 discloses the adhesive strength between an olefin layer and a polar resin layer, it does not disclose anything regarding improving the strength of a filler-reinforced olefin.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] Patent Document 6 discloses a filler-reinforced resin composition using a carbodiimide group-modified polypropylene as a compatibilizer and a molded article thereof, and describes that it is excellent in mechanical properties such as impact resistance and flexural strength as compared with a molded article of a resin composition using maleic anhydride-modified polypropylene as a compatibilizer. However, since the required performance level in the market has been rising, it has been found that there is room for further improvement in mechanical properties such as impact resistance and flexural strength.

[0008] An object of the present invention is to provide an auxiliary agent for a filler-reinforced resin that enables a molded article excellent in mechanical properties such as impact resistance and flexural strength to be obtained, and a filler-reinforced resin composition containing the auxiliary agent and a molded article thereof.

MEANS FOR SOLVING THE PROBLEMS

[0009] As a result of intensive studies, the present inventors have found that according to the following configuration examples, the above problems can be solved, and the present invention has been completed. The configuration examples of the present invention are as follows.

[0010] [1] An auxiliary agent for a filler-reinforced resin that satisfies the following requirements (i) to (ii). (i) At least one base polymer selected from polyolefins contains a graft-modified product graft-modified with a carbodiimide monomer represented by the following formula (1) or (2) (ii) Contains a carbodiimide group in an amount of 0.1 to 50 mmol per 100 g of the auxiliary agent for a filler-reinforced resin

[0011]

CHEMICAL FORMULA

[0012] [Chemical formula] [In formula (2), R 3 is a hydrogen atom or a methyl group, and R 4 is a hydrocarbon group which may have a substituent.]

[0013] [2] The filler-reinforced resin auxiliary agent according to [1], wherein the carbodiimide monomer is the carbodiimide monomer represented by the formula (1).

[0014] [3] In the formula (1), R 1 is a methyl group, R 2 is a branched alkyl group having no ring, m is 2, The filler-reinforced resin auxiliary agent according to [1] or [2].

[0015] [4] A filler-reinforced resin composition containing the filler-reinforced resin auxiliary agent according to any one of [1] to [3], an unmodified olefin resin (A), and a filler (B).

[0016] [5] The filler-reinforced resin composition according to [4], containing 0.01 to 50 parts by mass of the filler-reinforced resin auxiliary agent, 20 to 99 parts by mass of the unmodified olefin resin (A), and 1 to 80 parts by mass of the filler (B) (however, the total of (A) and (B) is 100 parts by mass).

[0017] [6] The base polymer before being graft-modified with the carbodiimide monomer is a propylene-based polymer, and the unmodified olefin-based resin (A) is a propylene-based resin (A1). The filler-reinforced resin composition according to [4] or [5].

[0018] [7] The filler-reinforced resin composition according to any one of [4] to [6], wherein the filler (B) is carbon fiber.

[0019] [8] A method for producing a filler-reinforced resin composition, comprising a step of reacting a filler-reinforcing resin auxiliary agent according to any one of [1] to [3] with a filler (B) in the presence of an unmodified olefin-based resin (A).

[0020] [9] A molded article obtained by molding the filler-reinforced resin composition according to any one of [4] to [7]. [Advantages of the Invention]

[0021] According to the present invention, it is possible to provide a filler-reinforcing resin auxiliary agent that enables the production of a molded article excellent in mechanical properties such as impact resistance and flexural strength, and a filler-reinforced resin composition containing the auxiliary agent. The obtained molded article can be suitably used for parts such as automobile parts that require particularly high rigidity, impact resistance, and durability. [Embodiments for Carrying Out the Invention]

[0022] [[Filler-Reinforcing Resin Auxiliary Agent]] The filler-reinforcing resin auxiliary agent according to one embodiment of the present invention (hereinafter also referred to as "this auxiliary agent") contains a graft-modified product (hereinafter also referred to as "this modified product") in which at least one base polymer selected from polyolefins is graft-modified with a carbodiimide monomer represented by the following formula (1) or (2), and the content of carbodiimide groups in 100 g of this auxiliary agent is 0.1 to 50 mmol. Since this auxiliary agent exhibits a strong interaction with the filler, it can improve the adhesion between the auxiliary agent and the filler in the filler-reinforced resin composition. Therefore, the molded article obtained by molding the composition is excellent in mechanical properties such as impact resistance and flexural strength.

[0023]

Chemical formula

[0024]

Chemical formula

[0025] In this auxiliary agent, the content of the carbodiimide group is 0.1 to 50 mmol, preferably 0.5 to 50 mmol, more preferably 1 to 50 mmol, per 100 g of the auxiliary agent. When the content of the carbodiimide group is within the above range, the auxiliary agent is excellent in the interaction with the filler. Specifically, the content of the carbodiimide group is measured and calculated by the method described in the following examples.

[0026] This auxiliary agent is not particularly limited as long as it includes this modified body, and the modified body used for this auxiliary agent may be one kind or two or more kinds. Since this modified body is a graft-modified body rather than a block copolymer or a random copolymer of an olefin monomer such as ethylene or propylene and the carbodiimide monomer, by using this modified body, this auxiliary agent exhibits the above effects.

[0027] The content of the modified product in this auxiliary agent is excellent in terms of the interaction with the filler, and in the filler-reinforced resin composition, it can improve the adhesion between the auxiliary agent and the filler in the composition, etc. Therefore, it is preferably 80 to 100% by mass, more preferably 90 to 100% by mass. This auxiliary agent preferably consists only of the modified product, but may also contain additives such as antioxidants and weather stabilizers in addition to the modified product.

[0028] <Modified product> This auxiliary agent contains a graft-modified product obtained by graft-modifying at least one base polymer selected from polyolefins with a carbodiimide monomer represented by the following formula (1) or (2). The modified product can also be said to be a graft-modified product containing at least one base polymer portion selected from polyolefins and a graft portion derived from a carbodiimide monomer represented by the following formula (1) or (2).

[0029] The grafting ratio in the modified product is preferably 0.3 to 7% by mass, more preferably 0.5 to 5% by mass, from the viewpoints that a graft-modified product with high grafting ease, high filler reinforcing property and high dispersion improvement effect of the modified product can be easily obtained, and the obtained graft-modified product does not become too hard. The grafting ratio is the mass of the structure derived from the carbodiimide monomer in the graft-modified product, 1 and can be determined by 1H-NMR measurement, specifically, by the method described in the following examples.

[0030] <Carbodiimide monomer> The carbodiimide monomer used for graft-modifying the base polymer is a compound represented by the following formula (1) or (2), and a compound represented by the following formula (1) is preferred from the viewpoints of the reactivity of the carbodiimide group, etc. Two or more kinds of carbodiimide monomers may be used for graft-modifying the base polymer, but usually one kind is used.

[0031] [Chemical formula] [In formula (1), R 1 is a hydrogen atom or a methyl group, R 2 is an alkyl group or an aryl group which may have a substituent, and m is an integer of 2 or more.]

[0032] [Chemical formula] [In formula (2), R 3 is a hydrogen atom or a methyl group, R 4 is a hydrocarbon group which may have a substituent.]

[0033] The carbodiimide monomer may be a monomer derived from biomass, a monomer derived from fossil fuel, or a monomer derived from both biomass and fossil fuel. In this specification, the raw material derived from biomass is a raw material made from any (renewable) natural raw material such as plant-derived or animal-derived, including fungi, yeast, algae and bacteria, and its residue. For example, as carbon 14 C isotope is contained at a ratio of about 1×10 -12 and the biomass carbon concentration (unit: pMC) measured according to ASTM D6866 is about 100 pMC. The raw material derived from biomass can be obtained, for example, by a conventionally known method.

[0034] In formula (1), R 1 is a hydrogen atom or a methyl group, and a methyl group is preferred in terms of easily obtaining this auxiliary agent which has excellent interaction with the filler.

[0035] In formula (1), R 2 is an alkyl group or an aryl group which may have a substituent. The alkyl group which may have a substituent may be chain-like (which may be straight-chain or have a branch), or may contain an alicyclic ring. The number of carbon atoms of the alkyl group which may have the substituent is preferably 1 or more, more preferably 3 or more, preferably 20 or less, more preferably 12 or less, and even more preferably 8 or less. Also, the number of carbon atoms of the aryl group which may have the substituent is preferably 5 or more, more preferably 6 or more, preferably 20 or less, more preferably 12 or less, and even more preferably 8 or less. Examples of the alicyclic ring include a cyclobutyl ring, a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and these rings having a hydrocarbon group. Further, the alicyclic ring may be a polycyclic ring such as an adamantyl ring or a methyladamantyl ring.

[0036] Examples of the substituent which the alkyl group and the aryl group may have include a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a carboxylic acid ester group having 1 to 8 carbon atoms, a sulfonic acid ester group having 1 to 8 carbon atoms, a carbonyl group having 1 to 8 carbon atoms, an amide group having 1 to 8 carbon atoms, an amino group having 1 to 8 carbon atoms, a sulfide group having 1 to 8 carbon atoms, a phosphate ester group having 1 to 8 carbon atoms, an alkylsilyl group having 1 to 8 carbon atoms, and an alkoxysilyl group having 1 to 8 carbon atoms.

[0037] Among these, the R 2 is preferably an alkyl group having a branch and no ring from the viewpoints that the stability of the carbodiimide group in air and upon heating is improved, the yield in synthesizing the modified product is increased, the production cost can be reduced, etc., and that an auxiliary agent excellent in interaction with the filler can be easily obtained, etc. More preferably, it is an alkyl group having 3 to 7 carbon atoms having a branch and no ring. In addition, when the R 2 has no ring, steric hindrance due to the ring structure is suppressed, and the reactivity of the carbodiimide group becomes good.

[0038] Preferable examples of the alkyl group having the branching and not having a ring include an isopropyl group, sec-butyl group, isobutyl group, tert-butyl group, 1-methylbutyl group, 1,2-dimethylpropyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1-methylpentyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 1,2,2-trimethylpropyl group, 2-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 3-methylpentyl group, 3,3-dimethylbutyl group, 4-methylpentyl group, 1-ethyl-2-methylpropyl group, 1-ethylbutyl group, 1,1-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-methylhexyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 1,2,3-trimethylbutyl group, 1,2,2-trimethylbutyl group, 1,3,3-trimethylbutyl group, 2-methylhexyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 2,3,3-trimethylbutyl group, 1,1-dimethylpentyl group, 1,1,2-trimethylbutyl group, 1,1,3-trimethylbutyl group, 1,1,2,2-tetramethylpropyl group, 2,2-dimethylpentyl group, 2,2,3-trimethylbutyl group, 3-methylhexyl group, 3,4-dimethylpentyl group, 3,3-dimethylpentyl group, 1-ethylpentyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 1-ethyl-2,2-dimethylpropyl group, 2-ethylpentyl group, 2-ethyl-3-methylbutyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-1,2-dimethylpropyl group, 3-ethylpentyl group, 1,1-diethylpropyl group, 2,2-diethylpropyl group, 1-propylbutyl group, diisopropylmethyl group, 1-isopropylbutyl group. Among these, from the viewpoint of easily obtaining an excellent auxiliary agent due to the interaction with the filler, the tert-butyl group is preferable.

[0039] In formula (1), m is an integer of 2 or more, and from the viewpoints of the solubility of the carbodiimide monomer, ease of availability, ease of purification of the obtained modified product, etc., it is preferably an integer of 2 to 6, more preferably an integer of 2 to 4, and particularly preferably 2.

[0040] In formula (2), R 3 is a hydrogen atom or a methyl group, and a hydrogen atom is preferred from the viewpoints of being able to easily obtain a modified product with a high grafting rate, etc.

[0041] In formula (2), R 4 is a hydrocarbon group which may have a substituent. Specific examples of the hydrocarbon group include an alkyl group or an aryl group which may have a substituent. The alkyl group which may have a substituent may be chain-like (which may be straight-chain or may have a branch), or may contain an alicyclic ring. The carbon number of the hydrocarbon group which may have a substituent is preferably 1 or more, more preferably 3 or more, preferably 20 or less, more preferably 12 or less, and still more preferably 8 or less. Examples of the substituent which the hydrocarbon group may have include, for example, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a carboxylic acid ester group having 1 to 8 carbon atoms, a sulfonic acid ester group having 1 to 8 carbon atoms, a carbonyl group having 1 to 8 carbon atoms, an amide group having 1 to 8 carbon atoms, an amino group having 1 to 8 carbon atoms, a sulfide group having 1 to 8 carbon atoms, a phosphate ester group having 1 to 8 carbon atoms, an alkylsilyl group having 1 to 8 carbon atoms, and an alkoxysilyl group having 1 to 8 carbon atoms.

[0042] Among these, as the above R 4 from the viewpoints of the solubility of the carbodiimide monomer, ease of availability, ease of purification of the obtained modified product, etc., it is preferably an alicyclic hydrocarbon group having 4 to 20 carbon atoms, and more preferably an alicyclic hydrocarbon group having 5 to 7 carbon atoms. Examples of the alicyclic ring include a cyclobutyl ring, a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and these rings having the above-described substituents. The alicyclic ring may also be a polycyclic ring such as an adamantyl ring or a methyladamantyl ring.

[0043] <Base polymer> The base polymer before being graft-modified with the carbodiimide monomer is at least one polymer selected from polyolefins. Specific examples of the olefin include cyclic olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-butene, and tetracyclododecene. The polyolefin may be a homopolymer of these olefins, a copolymer of two or more of these olefins, or a copolymer of one or more of these olefins and one or more of the comonomers described below. Among these, the polyolefin is preferably at least one polymer selected from ethylene-based polymers, propylene-based polymers, and butene-based polymers. When a solvent is used during the graft reaction, it is more preferably at least one polymer selected from ethylene-based polymers and propylene-based polymers from the viewpoints of excellent solubility in the solvent and excellent separability from impurities after the graft reaction. The base polymer of the modified product may be two or more kinds, but is usually one kind.

[0044] From the viewpoint that the effects of the present invention are more exhibited, etc., the base polymer is preferably a polymer having no at least one active hydrogen-containing group selected from a carboxy group, an acid anhydride group, an amino group, a hydroxy group, and a thiol group. Also, from the viewpoint that the effects of the present invention are more exhibited, etc., the base polymer is preferably a polymer having no group that can be easily converted into a group having active hydrogen such as a carboxylic acid derivative group such as an acid halide, an amide, an imide, an ester, or an epoxy group by water or the like.

[0045] The weight average molecular weight (Mw) of the base polymer is not particularly limited, but from the viewpoint of ease of synthesis of the modified product and the like, it is preferably 20,000 or more, more preferably 25,000 or more, and preferably 1,000,000 or less, more preferably 700,000 or less. The number average molecular weight (Mn) of the base polymer is not particularly limited, but for the same reason, it is preferably 10,000 or more, more preferably 15,000 or more, and preferably 500,000 or less, more preferably 300,000 or less. The molecular weight distribution (Mw / Mn) of the base polymer is not particularly limited, but it is preferably 1.5 or more, more preferably 2.0 or more, and preferably 7.0 or less, more preferably 6.0 or less. Specifically, the Mw and Mn are measured by the methods described in the following examples.

[0046] The base polymer can be synthesized by a conventionally known method, or a commercially available product may be used. The conventionally known method is not particularly limited, and examples thereof include a method using a coordination polymerization catalyst system containing a transition metal. Specifically, in the presence of a catalyst such as a magnesium chloride-supported titanium catalyst, a vanadium-based catalyst containing a soluble vanadium compound and an alkylaluminum halide compound, or a metallocene catalyst containing a metallocene compound and an organoaluminum oxy compound, an olefin such as ethylene or propylene and, if necessary, the comonomer are (co)polymerized to synthesize.

[0047] As the raw material of the base polymer (e.g., monomers such as olefins and comonomers described later), only a biomass-derived raw material may be used, only a fossil fuel-derived raw material may be used, or both a biomass-derived raw material and a fossil fuel-derived raw material may be used. It is preferable that the base polymer is a polymer using a biomass-derived raw material from the viewpoint of reducing the environmental load (mainly reducing greenhouse gas emissions).

[0048] [Ethylene-based polymer] The ethylene-based polymer is not particularly limited as long as the content of the structural unit derived from ethylene in the polymer is 50% by mass or more, and it may be a homopolymer of ethylene or a copolymer of ethylene and a comonomer. In the case of a copolymer, its structure is not particularly limited.

[0049] Examples of the comonomer include at least one monomer selected from propylene, α-olefins having 4 to 20 carbon atoms, and conjugated polyenes. Among these, propylene and α-olefins having 4 to 20 carbon atoms are preferred. The α-olefin having 4 to 20 carbon atoms may be linear or branched, and examples thereof include 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. The content of the structural unit derived from the comonomer in the ethylene-based polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less from the viewpoints of being less likely to cause blocking of pellets and powders and being easy to handle. In this specification, a polymer having a content of the structural unit derived from ethylene of 50% by mass and a content of the structural unit derived from propylene or butene of 50% by mass is within the category of ethylene-based polymers.

[0050] [Propylene-based polymer] The propylene-based polymer is not particularly limited as long as the content of the structural unit derived from propylene in the polymer is 50% by mass or more, and it may be a homopolymer of propylene or a copolymer of propylene and a comonomer. The structure of these (co)polymers is not particularly limited.

[0051] Examples of the comonomer include at least one monomer selected from ethylene, α-olefins having 4 to 20 carbon atoms, and conjugated polyenes. Among these, ethylene and α-olefins having 4 to 20 carbon atoms are preferable. Examples of the α-olefins having 4 to 20 carbon atoms include the same α-olefins as those described in the section on ethylene-based polymers. From the viewpoints of being less likely to cause blocking of pellets or powders and being easy to handle, the content of the constitutional unit derived from the comonomer in the propylene-based polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. In this specification, a polymer in which the contents of both the constitutional unit derived from propylene and the constitutional unit derived from butene are 50% by mass falls within the category of propylene-based polymers.

[0052] [Butene-based polymer] The butene-based polymer is not particularly limited as long as the content of the constitutional unit derived from butene in the polymer is 50% by mass or more, and it may be a homopolymer of butene, particularly 1-butene, or a copolymer of butene (particularly 1-butene) and a comonomer. The structure of these (co)polymers is not particularly limited.

[0053] Examples of the comonomer include at least one monomer selected from ethylene, propylene, α-olefins having 5 to 20 carbon atoms, and conjugated polyenes. Among these, ethylene, propylene, and α-olefins having 5 to 20 carbon atoms are preferable. Examples of the α-olefins having 5 to 20 carbon atoms include the same α-olefins as those described in the section on ethylene-based polymers. From the viewpoints of being less likely to cause blocking of pellets or powders and being easy to handle, the content of the constitutional unit derived from the comonomer in the butene-based polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

[0054] <Synthesis method of the modified product> The method for synthesizing the modified product is not particularly limited, and there is no particular limitation as long as a graft-modified product obtained by graft-modifying the base polymer with the carbodiimide monomer can be obtained. However, from the viewpoint of easily synthesizing the modified product, etc., a method of adding a radical initiator and the carbodiimide monomer to a solution in which the base polymer is dissolved or dispersed in a solvent, preferably a solution in which the base polymer is dissolved in an organic solvent, and reacting (graft reaction) is preferred. In addition, when using a reaction apparatus having a stirring ability capable of uniformly flowing the base polymer, a solvent may not be used. According to the above method, since graft polymerization occurs, a graft-modified product can be obtained.

[0055] The amount of the carbodiimide monomer used in the graft reaction is preferably 10 to 1000 moles, more preferably 10 to 800 moles, per mole of the base polymer, from the viewpoint of easily obtaining the modified product having a graft ratio within the above range and suppressing the formation of a polymer of the carbodiimide monomer itself (hereinafter also referred to as "non-grafted polymer").

[0056] Examples of the radical initiator include organic peroxides and azo compounds. Specifically, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxybenzoate) hexyne-3, 1,4-bis(tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di-(tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate, tert-butyl perdiethylacetate, tert-butyl peroxyisopropyl monocarbonate (tert-butyl peroxyisopropyl monocarbonate) and other organic peroxides; azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate. Among these, organic peroxides such as dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane, 1,4-bis(tert-butylperoxyisopropyl) benzene, and tert-butyl peroxyisopropyl monocarbonate are preferred. One kind of the radical initiator may be used, or two or more kinds may be used.

[0057] The amount of the radical initiator used in the graft reaction is preferably 0.01 mol or more, more preferably 0.05 mol or more, and preferably 0.7 mol or less, more preferably 0.5 mol or less, per 1 mol of the carbodiimide monomer, from the viewpoints that the graft reaction occurs efficiently and the modified product having a graft ratio within the above range can be easily obtained.

[0058] As the organic solvent, an organic solvent that does not significantly inhibit the graft reaction of the carbodiimide monomer and has an affinity with the base polymer in the temperature range where the graft reaction is carried out is preferable. Specific examples of such organic solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, and decane; alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and decahydronaphthalene; chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, and tetrachloroethylene; alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate; and ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran, and dioxyanisole. Also, suspension polymerization and emulsion polymerization can be carried out using water as the solvent. These solvents may be used alone or in combination of two or more. In addition, it is preferable that the reaction solution becomes a homogeneous phase by using these solvents, but it may also be a non-uniform plurality of phases.

[0059] In order to carry out the graft reaction in a region where the liquid containing the base polymer can be homogeneously stirred, the concentration of the base polymer in the liquid is usually set to 50 to 1000 g / L, but in order to achieve a high graft ratio, it is preferably 200 to 1000 g / L.

[0060] The radical initiator and the carbodiimide monomer may initiate the graft reaction by adding them all at once to the liquid containing the base polymer (or the base polymer itself), but in order to achieve a high graft ratio, it is preferable to carry out the graft reaction by sequentially adding them over about 0.1 to 5 hours. In addition, when a radical initiator and a carbodiimide monomer are added to a base polymer or a solution in which the base polymer is dissolved or dispersed in a solvent, the order of addition thereof is not particularly limited. For example, when these are added sequentially as described above, the radical initiator and the carbodiimide monomer may be added sequentially, or the carbodiimide monomer may be added first and then the radical initiator may be added sequentially.

[0061] The graft reaction is preferably carried out at a temperature of usually 60°C or higher, preferably 100°C or higher, usually 200°C or lower, preferably 160°C or lower, for usually 2 hours or longer, preferably 3 hours or longer, usually 10 hours or shorter, preferably 8 hours or shorter. When the graft reaction is carried out within the above temperature and time ranges, it is preferable because the base polymer can be sufficiently dissolved in the solvent and the radical initiator used can be decomposed within several hours.

[0062] The modified product obtained by the graft reaction may be purified and isolated by known methods such as filtration, centrifugation, reprecipitation, and / or washing, using the solvent used, unreacted radical initiator, carbodiimide monomer, by-produced ungrafted polymer, and the like. In this case, from the viewpoint of easily obtaining the present auxiliary agent having excellent interaction with the filler, etc., it is desirable to purify and isolate so that the content of the ungrafted polymer contained in the modified product is preferably 5% by mass or less, more preferably 2% by mass or less.

[0063] ≪Filler-reinforced resin composition≫ The filler-reinforced resin composition according to one embodiment of the present invention (hereinafter also referred to as "the present composition") contains the present auxiliary agent, an unmodified olefin-based resin (A), and a filler (B).

[0064] <The present auxiliary agent> The present auxiliary agent used in the present composition may be one kind or two or more kinds. The content of the present auxiliary agent in the present composition is preferably 0.01 to 50 parts by mass, more preferably 0.05 to 30 parts by mass, and still more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the resin (A) and the filler (B). When the content of the present auxiliary agent is within the above range, the interaction between the present auxiliary agent and the filler in the present composition can be improved, and a molded article excellent in mechanical properties such as impact resistance and flexural strength can be easily obtained.

[0065] It is preferable to use the present composition so that the content of the carbodiimide group per 100 g of the present composition falls within the following range, since it can improve the interaction with the filler. The content of the carbodiimide group per 100 g of the present composition is usually 0.0001 to 40 mmol, preferably 0.0005 to 35 mmol, and still more preferably 0.001 to 30 mmol.

[0066] <Unmodified olefin resin (A)> Examples of the unmodified olefin resin (A) (hereinafter also simply referred to as "resin (A)") include the same resins as the polyolefins listed in the column of the base polymer. Further, it may be selected from conventionally known olefin resins depending on the use, purpose, type of filler, etc. The resin (A) used in the present composition may be one kind or two or more kinds.

[0067] The resin (A) refers to a resin in which an olefin resin is not substantially modified with a compound containing a polar group such as an ether bond (including a hydroxy group, an alkoxy group, etc.), a carbonyl group (including a carboxy group, an ester bond, etc.), an amino group, or an epoxy group. Here, not being substantially modified means that the amount of modification is less than 0.05 mmol equivalent in terms of polar groups, more preferably 0.01 mmol equivalent or less, particularly preferably 0.001 mmol equivalent or less, and most preferably 0.0001 mmol equivalent or less. It is preferable that the resin (A) is not modified at all with the compound containing the polar group in the olefin resin.

[0068] Examples of the resin (A) include ethylene-α-olefin copolymers such as low-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, and ethylene-octene copolymer; ethylene-polar group-containing vinyl copolymers; polybutene-1; poly-4-methyl-1-pentene; poly-3-methyl-1-butene; cyclic polyolefins such as ethylene-tetracyclododecene copolymer; and rubbers such as ethylene-propylene-butene terpolymer rubber. Further, ethylene-propylene-non-conjugated diene copolymer rubbers (EPDM) using non-conjugated dienes such as 5-ethylidene norbornene, 5-methyl norbornene, 5-vinyl norbornene, dicyclopentadiene, and 1,4-pentadiene are also preferably used.

[0069] Among these, when the present composition is used for applications such as use at a high temperature close to 100°C or direct contact with substances such as gasoline and oil that swell olefin resins, it is desirable to use olefin resins with high melting points and crystallinity such as polypropylene, high-density polyethylene, and linear low-density polyethylene.

[0070] The resin (A) may be in the form of either a so-called resin or an elastomer, and both isotactic and syndiotactic structures can be used, and there are no particular restrictions on stereoregularity. It is also possible to directly use commercially available resins.

[0071] The resin (A) can be synthesized by any conventionally known method, and for example, it can be polymerized using a titanium-based catalyst, a vanadium-based catalyst, a metallocene catalyst, or the like. As the raw material of the resin (A), a resin using only a biomass-derived raw material, a resin using only a fossil fuel-derived raw material, or a resin using both a biomass-derived raw material and a fossil fuel-derived raw material may be used.

[0072] When the base polymer before being graft-modified with the carbodiimide monomer is a propylene-based polymer, as the resin (A), a propylene-based resin (A1) is preferred. Examples of the propylene-based resin (A1) include a propylene homopolymer and a propylene / α-olefin copolymer, and those having any stereostructure such as isotactic and syndiotactic may be used. The content of the constituent unit derived from α-olefin in the propylene / α-olefin copolymer is usually more than 0 mol% and 30 mol% or less, preferably more than 0 mol% and 20 mol% or less, and more preferably more than 0 mol% and 10 mol% or less.

[0073] The content of the resin (A) in the present composition is preferably 20 to 99 parts by mass, more preferably 30 to 95 parts by mass, and still more preferably 50 to 90 parts by mass with respect to a total of 100 parts by mass of the resin (A) and the filler (B). When the content of the resin (A) is within the above range, a molded article in which the physical properties of the resin (A) are sufficiently exhibited can be easily obtained, and a molded article excellent in mechanical properties such as impact resistance and flexural strength can be easily obtained.

[0074] <Filler (B)> Examples of the filler (B) include an inorganic filler and an organic filler. The filler (B) used in the present composition may be one kind or two or more kinds.

[0075] Examples of the inorganic filler include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, calcium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass bead, calcium silicate, montmorillonite, bentonite, boron fiber, carbon fiber, carbon black, carbon nanofiber, aluminum powder, molybdenum sulfide, and the like. These inorganic fillers may be fillers obtained by treating the inorganic fillers with an organic substance or the like.

[0076] Examples of the organic filler include fibers such as wholly aromatic polyamide fiber, aliphatic polyamide fiber, polyester fiber, and cellulose fiber, and fine dispersions such as liquid crystal polyester and polyamide. Further, fillers obtained by decomposing plants into fibrous or powdery forms are also included.

[0077] The content of the filler (B) in the present composition is preferably 1 to 80 parts by mass, more preferably 5 to 70 parts by mass, and still more preferably 10 to 50 parts by mass with respect to 100 parts by mass in total of the resin (A) and the filler (B). When the content of the filler (B) is within the above range, a molded article in which the reinforcing effect of the filler (B) is sufficiently exhibited can be easily obtained, and a molded article excellent in mechanical properties such as impact resistance and flexural strength can be easily obtained. For example, when the filler (B) in the present composition is carbon fiber, if the content is less than 1 part by mass, the reinforcing effect of the resin by the carbon fiber may not appear, and if the content exceeds 80 parts by mass, the toughness may be lost.

[0078] (Carbon fiber) Carbon fiber can be cited as a filler (B) effective for strengthening the resin (A). When carbon fiber is used as the filler (B), a composite material can be obtained that has the same strength as conventional carbon fiber reinforced engineering plastics but can be lightweighted, and the composition has advantages such as excellent fluidity during molding and being suitable for thinning of the resulting molded body, and such a composition can be easily obtained.

[0079] As the carbon fiber, various conventionally known carbon fibers can be used. Specifically, carbon fibers such as polyacrylonitrile-based, rayon-based, pitch-based, polyvinyl alcohol-based, and regenerated cellulose-based can be cited.

[0080] The average fiber diameter of the carbon fiber is preferably 3 to 30 μm, more preferably 4 to 15 μm. When using carbon fiber with a fiber diameter in the above range, the fiber is difficult to break, and a composition in which the reinforcing effect of the carbon fiber is sufficiently exerted can be obtained with good productivity.

[0081] The average fiber length of the carbon fiber is usually 0.05 to 200 mm, preferably 0.2 to 50 mm, more preferably 4 to 20 mm. When using carbon fiber with a fiber length in the above range, the reinforcing effect of the resin by the carbon fiber tends to be sufficiently exerted.

[0082] The average aspect ratio of the carbon fiber is preferably 5 to 6000, more preferably 30 to 3000, and even more preferably 100 to 2000. When using carbon fiber with an aspect ratio in the above range, a composition excellent in strength and moldability can be easily obtained. The aspect ratio of the carbon fiber can be obtained by average fiber length / average fiber diameter from the average fiber diameter and the average fiber length.

[0083] Chopped strands can also be used as the carbon fiber. The length of this chopped strand is usually 1 to 20 mm, and the fiber diameter is usually about 3 to 30 μm, preferably 4 to 10 μm.

[0084] As the carbon fiber, fibers subjected to surface treatment such as oxidation etching or coating are preferred. Examples of the oxidation etching treatment include air oxidation treatment, oxygen treatment, treatment with an oxidizing gas, treatment with ozone, corona treatment, flame treatment, (atmospheric pressure) plasma treatment, treatment with an oxidizing liquid (nitric acid, aqueous solution of alkali metal hypochlorite, potassium dichromate-sulfuric acid, potassium permanganate-sulfuric acid), etc. Examples of the substance for coating the carbon fiber include carbon, silicon carbide, silicon dioxide, silicon, plasma monomer, ferrocene, iron trichloride, etc.

[0085] <Additive> In the present composition, conventional known additives other than the present auxiliary agent, resin (A) and filler (B) may be used as long as the object of the present invention is not impaired. Examples of the additive include other resins other than the resin (A), softening agents, tackifiers, anti-aging agents, processing aids, adhesion improvers, heat stabilizers, weather stabilizers, antistatic agents, colorants, lubricants, flame retardants, blooming inhibitors. The additive may be an additive using only a biomass-derived raw material as its raw material, an additive using only a fossil fuel-derived raw material, or an additive using both a biomass-derived raw material and a fossil fuel-derived raw material. Each of the additives may be used alone or in combination of two or more.

[0086] Examples of the other resin include vinyl resins, polystyrene, polyamide, acrylic resins, polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene oxide, polyimide, polyether imide, acrylonitrile-butadiene-styrene copolymer (ABS), styrene-based rubbers, conjugated diene-based rubbers, phenol resins, melamine resins, silicone resins, epoxy resins. Among these, styrene-based rubbers are preferred, and specifically, styrene-butadiene-styrene-based SBS rubbers, styrene-butadiene-butylene-styrene-based SBBS rubbers, styrene-ethylene-butylene-styrene-based SEBS rubbers, etc. can be mentioned.

[0087] <Preparation method of this composition> The preparation method of this composition is not particularly limited as long as a composition containing the said auxiliary agent, resin (A) and filler (B) can be prepared, and a conventionally well-known method can be adopted. However, it is preferable to prepare by melt-kneading the said auxiliary agent, resin (A) and filler (B). The composition obtained by such a method has the filler (B) very well dispersed in the resin (A), and has excellent adhesion at the interface between the resin (A) and the filler (B), and is excellent in the balance of mechanical properties such as impact resistance, rigidity, and heat resistance.

[0088] Examples of preparing this composition by melt-kneading are shown below. The said auxiliary agent, resin (A), filler (B) and the said additive used as necessary are charged into a Henschel mixer, V-type blender, tumbler blender, ribbon blender, etc. simultaneously or sequentially, kneaded, and then melt-kneaded with a single-screw extruder, multi-screw extruder, kneader, Banbury mixer, etc., whereby this composition can be prepared. Among these, it is preferable to use a device with excellent kneading performance such as a multi-screw extruder, kneader, Banbury mixer, etc. because a composition in which each component is more uniformly dispersed and reacted can be easily prepared.

[0089] The said auxiliary agent, resin (A), filler (B) and the said additive used as necessary can take either a method of pre-mixing and then supplying from a hopper, or a method of supplying some components from a hopper and supplying the remaining components from a supply port installed at an arbitrary part between the hopper part and the tip of the extruder.

[0090] The temperature during the melt-kneading is preferably equal to or higher than the highest melting point among the melting points of the respective components to be mixed. Specifically, melt-kneading is usually carried out in the range of 150 to 300°C, preferably 200 to 280°C.

[0091] ≪Formed body≫ The formed body according to one embodiment of the present invention is a formed body obtained by forming the present composition. At the time of this forming, the present composition may be formed as it is, or may be formed by (dry) blending with a diluent or the like. Any known forming method can be used. Specifically, injection molding, blow molding, press molding, calender molding, extrusion molding, stamping mold molding, etc. may be mentioned. At the time of these moldings, conventionally known molding apparatuses can be used. As the molding method, an injection molding method and a press molding method are particularly preferable.

[0092] The shape of the formed body is not particularly limited and may be any shape suitable for the desired use. For example, a film (including plate-like bodies such as sheets, which may be stretched or unstretched), a pipe, a tube, a fiber (filament), a mold stamping formed body may be mentioned. The stretched film can be produced, for example, by stretching an extruded film (unstretched) by, for example, a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), a simultaneous biaxial stretching method, or a uniaxial stretching method. The fiber can be produced, for example, by extruding the melted present composition through a spinneret.

[0093] It is preferable that the shape of the filler (B) used as a raw material is maintained in the filler present in the formed body during the process of manufacturing the present composition and the formed body. For example, when using carbon fibers as the filler (B), the average fiber length of the carbon fibers present in the molded article is usually 0.01 mm or more, preferably 0.1 mm or more, more preferably 1 mm or more, from the viewpoint of easily obtaining a molded article excellent in rigidity, impact resistance, durability, etc. Although the longer the average fiber length of the carbon fibers, the better, it is usually 20 mm or less, preferably 15 mm or less.

[0094] The molded article is used in a wide range of applications from household goods to industrial goods. Specifically, electrical components, electronic components, automotive parts, mechanical mechanism parts, food containers, films, fibers, etc. can be mentioned. More specifically, for example, office and OA equipment such as printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, facsimiles, copiers, ECRs (electronic cash registers), calculators, electronic notebooks, electronic dictionaries, cards, holders, stationery, etc.; home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, game machines, irons, kotatsu, etc.; AV equipment such as TVs, VTRs, video cameras, cassette players, tape recorders, mini discs, CD players, speakers, liquid crystal displays, etc.; electrical and electronic components and communication equipment such as connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulation materials, electric wires, cables, transformers, deflection yokes, distribution boards, clocks, etc.

[0095] In addition, examples of the molded article include covers such as seats (padding, upholstery, etc.), belts, ceiling coverings, convertible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, tires, wheel covers, mattress covers, etc.; airbags, (electrical) insulating materials, hanging handles, hanging straps, wire sheathing materials, coating materials, overlay materials, floor materials, corner walls, deck panels, plywood, ceiling boards, partition boards, side walls, carpets, wallpapers, wall finishing materials, exterior materials, interior materials, roofing materials, sound insulation boards, heat insulation boards, window materials, etc. for vehicles (including automobiles), ships, aircraft, and building materials; and life and sports goods such as clothing, curtains, sheets, plywood, synthetic fiber boards, rugs, entrance mats, seats, buckets, hoses, containers, glasses, bags, cases, goggles, ski boards, rackets, tents, musical instruments, etc.

[0096] Furthermore, examples of the molded body include bottles for shampoos, detergents, etc., seasoning bottles for edible oils, soy sauces, etc., beverage bottles for mineral waters, juices, etc., heat-resistant food containers such as lunch boxes, bowls for steamed eggs, tableware such as plates and chopsticks, various other food containers, packaging films, packaging bags, and the like.

Examples

[0097] Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples insofar as the gist thereof is not exceeded.

[0098] <Melt Flow Rate (MFR)> Measurement was carried out at 230°C under a load of 2.16 kg in accordance with ASTM D1238.

[0099] <Grafting Ratio 1> Using a Bruker BioSpin Co., Ltd. AVANCEIIIcryo-500 type nuclear magnetic resonance apparatus (500 MHz), measurement solvent: 1,1,2,2-tetrachloroethane-d2, measurement temperature: 120°C, spectral width: 20 ppm, pulse repetition time: 7.0 seconds, pulse width: 5.00 μsec (45° pulse), the 1 1H-NMR spectrum of the MACDI-PP synthesized in Synthesis Example 1 below was measured. In the obtained spectrum, from the peak intensity ratio of the protons of the hydrocarbon groups bonded to the carbodiimide groups present at 3.0 ppm to 4.0 ppm and the protons of all the hydrocarbon groups derived from the base polymer present at 0.3 ppm to 2.5 ppm, the grafting ratio of the MACDI-PP synthesized in Synthesis Example 1 below was calculated.

[0100] <Grafting Ratio 2> The grafting ratio of maleic anhydride in the MAH-PP synthesized in Synthesis Example 2 below was measured by the following method using FT-IR. After preparing a sheet by hot pressing the sample at 250°C for 3 minutes, the transmission method was used at 1790 cm using an infrared spectrophotometer (FT-IR410 type, manufactured by JASCO Corporation).-1 The near-infrared absorption spectrum was measured. The measurement conditions were a resolution of 2 cm -1 and an integration time of 32 times.

[0101] <Weight-average molecular weight (Mw) and number-average molecular weight (Mn)> Mw and Mn were measured under the following conditions using an HLC-8321GPC / HT type gel permeation chromatograph (GPC) manufactured by Tosoh Corporation. Separation column: TSKgel GMH6-HT (2 columns) and TSKgel GMH6-HTL (2 columns) (both 7.5 mm I.D. × 30 cm, manufactured by Tosoh Corporation) Column temperature: 140 °C Mobile phase: o-dichlorobenzene (containing 0.025 mass% dibutylhydroxytoluene (BHT)) Elution rate: 1.0 mL / min Sample concentration: 0.1% (w / v) Sample injection volume: 0.4 mL Detector: Differential refractometer Calibration of the apparatus: Calibration was performed using monodisperse polystyrene (manufactured by Tosoh Corporation, #3stdset).

[0102] [Synthesis Example 1] Synthesis of MACDI-PP Into a 500 mL separable flask, 15.0 g of polypropylene (manufactured by Prime Polymer Co., Ltd., trade name: F327) and 62 mL of xylene were charged. After replacing the atmosphere in the separable flask with nitrogen, the internal temperature was raised to 120 °C, and while maintaining this temperature, 22.1 mmol of ethyl methacrylate-tert-butylcarbodiimide was charged. Next, 9.2 mmol of tert-butylperoxyisopropyl monocarbonate (Perbutyl I, manufactured by NOF Corporation) dissolved in 10 mL of xylene was fed over 10 minutes while stirring at a stirring speed of 400 rpm using a double anchor blade. Thereafter, after further stirring for 3 hours, 150 mL of xylene was fed to dilute the reaction solution. Thereafter, the internal temperature of the separable flask was cooled to 50 °C, and the slurry-like reaction solution was taken out. 400 mL of acetone was added to the obtained reaction solution and stirred for 10 minutes. Then, the stirred solution was filtered to separate it into a solid content and a filtrate. The steps from adding this acetone to the obtained solid content to filtration were repeated 3 more times. By these 4 filtrations, unreacted ethyl methacrylate-tert-butylcarbodiimide and the homopolymer of ethyl methacrylate-tert-butylcarbodiimide were removed. The solid content after the 4th filtration was dried in a vacuum dryer at 90 °C for 10 hours to obtain 15.37 g of a graft-modified product (hereinafter abbreviated as "MACDI-PP"). The grafting rate in the obtained MACDI-PP was 1.3 mass%.

[0103] [Synthesis Example 2] Synthesis of MAH-PP 100 parts by mass of polypropylene (manufactured by Prime Polymer Co., Ltd., trade name: F327), 1 part by mass of maleic anhydride (manufactured by Fujifilm Wako Pure Chemical Corporation, hereinafter abbreviated as "MAH"), and 0.25 part by mass of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexine-3 (manufactured by NOF Corporation, trade name: Perhexyne 25B) were mixed and extruded using a twin-screw kneader (manufactured by Japan Steel Works, Ltd., TEX-30, L / D = 40, using a vacuum vent) under the conditions of a cylinder temperature of 220 °C, a screw rotation speed of 200 rpm, and a discharge rate of 80 g / min to obtain maleic acid-modified polypropylene. The obtained maleic acid-modified polypropylene was dissolved in xylene, and then the obtained xylene solution was poured into acetone to reprecipitate and purify the maleic acid-modified polypropylene to obtain "MAH-PP". The grafting rate of maleic anhydride in the obtained MAH-PP was 0.7 mass%.

[0104] [Example 1] The MACDI-PP obtained in Synthesis Example 1 was used as an auxiliary agent for filler-reinforced resin (hereinafter abbreviated as "Auxiliary Agent X"). The content of carbodiimide groups per 100 g of Auxiliary Agent X (mmol / 100 g) was calculated from the following formula (I), and the value was 6.2 mmol / 100 g. Content of carbodiimide group per 100 g of the auxiliary agent for filler-reinforced resin = (Grafting ratio of the graft-modified product used in the auxiliary agent for filler-reinforced resin [mass%] / Molecular weight of the carbodiimide monomer used in the synthesis of the graft-modified product) × 100 × 100 / 10 ··· (I)

[0105] [Comparative Example 1] 100 parts by mass of the MAH-PP obtained in Synthesis Example 2 and 8.8 parts by mass of a carbodiimide group-containing compound (manufactured by Nisshinbo Chemical Inc., trade name: Carbodilite HMV-8CA, carbodiimide group equivalent: 278, Mn: 2500) were each mixed, and using a twin-screw kneader (manufactured by Nippon Steel Works, Ltd., TEX-30, L / D = 40, using a vacuum vent), extrusion was carried out under the conditions of a cylinder temperature of 250 °C, a screw rotation speed of 200 rpm, and a discharge rate of 80 g / min to obtain an auxiliary agent for filler-reinforced resin (hereinafter abbreviated as "auxiliary agent CX-1").

[0106] The MFR (230 °C, 2.16 kg load) of the obtained auxiliary agent CX-1 was 130 g / 10 min. In addition, in the same manner as the grafting ratio 2, when analyzed by IR, since the peak derived from maleic acid had disappeared, the reaction rate was 100%. Further, when the content of the carbodiimide group per 100 g of the auxiliary agent CX-1 was calculated from the charged amount of the carbodiimide group-containing compound, the value was 27 mmol / 100 g.

[0107] [Comparative Example 2] The MAH-PP obtained in Synthesis Example 2 was used as an auxiliary agent for filler-reinforced resin (hereinafter abbreviated as "auxiliary agent CX-2").

[0108] [Example 2] 1 part by mass of auxiliary agent X, 79 parts by mass of resin A-1, and 20 parts by mass of filler B-1 were each mixed, and using a twin-screw kneader (manufactured by Technovel Corporation, KZW-15, L / D = 30), extrusion was carried out under the conditions of a cylinder temperature of 230 °C, a screw rotation speed of 130 rpm, and a discharge rate of 3 kg / h to obtain a filler-reinforced resin composition. The filler-reinforced resin composition obtained above was molded using an injection molding machine (manufactured by Shibaura Machine Co., Ltd., EC75SXIII) under the conditions of a cylinder temperature of 230°C, a mold temperature of 40°C, and a cooling time of 20 seconds to obtain a molded article.

[0109] [Examples 3 to 6 and Comparative Examples 3 to 4] A filler-reinforced resin composition and a molded article were obtained in the same manner as in Example 1, except that the raw materials described in the formulation column of Table 1 were used in the amounts (numerical values, parts by mass) described in the formulation column of Table 1.

[0110] [Unmodified olefin resin (A) used] The unmodified olefin resin (A) used in Examples 2 to 6 and Comparative Examples 3 to 4 is shown below. "Resin A-1": Polypropylene (trade name: J106G, manufactured by Prime Polymer Co., Ltd., MFR (230°C, 2.16 kg load) = 15 g / 10 min)

[0111] [Filler used] The fillers used in Examples 2 to 6 and Comparative Examples 3 to 4 are shown below. "Filler B-1": Carbon fiber (trade name: HT C205 6MM, epoxy sizing, manufactured by Teijin Limited) "Filler B-2": Carbon fiber (trade name: HT C605 6MM, nylon sizing, manufactured by Teijin Limited) "Filler B-3": Carbon fiber (trade name: HT C702 6MM, urethane sizing, manufactured by Teijin Limited)

[0112] <Izod impact strength> From the molded articles obtained in Examples 2 to 6 and Comparative Examples 3 to 4, test pieces (with processed notches) having a thickness of 1 / 8 inch were cut out, and using these test pieces, the Izod impact strength was measured at 23°C in accordance with ASTM D256. The results are shown in Table 1.

[0113] <Flexural strength> From the molded articles obtained in Examples 2 to 6 and Comparative Examples 3 to 4, test pieces having a length of 2.5 inches, a width of 1 / 2 inch, and a thickness of 1 / 8 inch were cut out, and using these test pieces, a three-point bending test was conducted under the conditions of a span of 48 mm, a compression speed of 5 mm / min, and a temperature of 23°C, and the bending strength was measured. The results are shown in Table 1.

[0114]

Table 1

Claims

1. An auxiliary agent for filler-reinforced resin that satisfies the following requirements (i) to (ii). (i) It contains a graft-modified product in which at least one base polymer selected from polyolefins is graft-modified with a carbodiimide monomer represented by the following formula (1) or (2). (ii) It contains 0.1 to 50 mmol of carbodiimide groups per 100 g of the auxiliary agent for filler-reinforced resin. 【Chemical 1】 [In formula (1), R 1 is a hydrogen atom or a methyl group, R 2 is an alkyl group or an aryl group which may have a substituent, and m is an integer of 2 or more.] [Chemical 2] [In formula (2), R 3 is a hydrogen atom or a methyl group, and R 4 is a hydrocarbon group which may have a substituent.]

2. The auxiliary agent for filler-reinforced resin according to Claim 1, wherein the carbodiimide monomer is the carbodiimide monomer represented by the formula (1).

3. In the formula (1), R 1 is a methyl group, R 2 is an alkyl group having a branch and no ring, m is 2. The auxiliary agent for filler-reinforced resin according to Claim 2.

4. A filler-reinforced resin composition containing the auxiliary agent for filler-reinforced resin according to Claim 1, an unmodified olefin resin (A), and a filler (B).

5. The filler-reinforced resin composition according to Claim 4, containing 0.01 to 50 parts by mass of the auxiliary agent for filler-reinforced resin, 20 to 99 parts by mass of the unmodified olefin resin (A), and 1 to 80 parts by mass of the filler (B) (however, the total of (A) and (B) is 100 parts by mass).

6. The filler-reinforced resin composition according to Claim 4, wherein the base polymer before being graft-modified with the carbodiimide monomer is a propylene-based polymer, and the unmodified olefin resin (A) is a propylene-based resin (A1).

7. The filler-reinforced resin composition according to Claim 4, wherein the filler (B) is carbon fiber.

8. A method for producing a filler-reinforced resin composition, including a step of reacting the auxiliary agent for filler-reinforced resin according to any one of Claims 1 to 3 with a filler (B) in the presence of an unmodified olefin resin (A).

9. A molded article formed by molding the filler-reinforced resin composition according to any one of Claims 4 to 7.

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