JP2019172798A - Carbon fiber reinforced resin composition and molded product thereof - Google Patents

Abstract

An object of the present invention is to provide a carbon fiber reinforced resin composition capable of obtaining CFRP (molded product) having improved physical properties such as rigidity, bending characteristics and impact resistance while maintaining good moldability. A carbon fiber reinforced resin composition comprising carbon fiber, a polyolefin resin, an olefin soft resin component and an adhesion promoter as essential components, wherein the olefin soft resin component comprises (1) 230 ° C., 21 The MFR measured at .18 N was 5 to 150 g / 10 min, and (2) the morphology when mixed with the polyolefin resin was such that the polyolefin resin was a continuous phase and the olefin soft resin component was a dispersed phase. Satisfying that a sea-island structure is formed and the average length of the dispersed phase is 0.1 to 10 μm, and that the blending ratio of the carbon fiber is 10 to 50% by mass based on the total of the essential components. The carbon fiber reinforced resin composition characterized by the above. [Selection diagram] Fig. 1

Description

  The present invention relates to a carbon fiber reinforced resin composition using a polyolefin-based resin as a matrix resin, and in particular, a carbon fiber reinforced plastic capable of obtaining a carbon fiber reinforced plastic (CFRP) having improved physical properties such as rigidity, bending characteristics and impact resistance. The present invention relates to a resin composition.

  In recent years, carbon fiber reinforced plastics (CFRP) among FRPs are attracting attention as lightweight structural materials because of their large specific elastic modulus and specific strength compared to iron and the like. In particular, in the fields of automobile materials and electronic materials, CFRP is being studied as an alternative material for metal materials and glass fiber reinforced plastic (GFRP).

  CFRP can be roughly classified into two types depending on the type of plastic used. One is CFRTS using a thermosetting resin, and the other is CFRTP (carbon fiber reinforced thermoplastic resin) using a thermoplastic resin.

  CFRTP is generally produced at a relatively low cost by combining it with discontinuous carbon fibers, taking advantage of its good moldability, including that it can be molded in a short time and has secondary workability. And suitable as a member requiring a complicated shape. In particular, CFRP using a polypropylene matrix resin has begun to attract attention because it can be molded at high speed and can be easily recycled.

  In general, polyolefins represented by polypropylene (PP) have poor adhesion to fillers. Thus, for example, a method for improving the adhesion between the polyolefin and the filler using acid-modified PP graft-modified with maleic anhydride or the like is disclosed (Patent Document 1). However, this method is an effective means for glass fibers (GF), but it cannot be said to be sufficiently effective for carbon fibers having no silanol group on the surface.

  In order to improve the interfacial adhesion between the polyolefin resin and the carbon fiber, a method of adding an acid-modified polyolefin resin is disclosed (Patent Document 2). However, further improvement has been demanded to satisfy practical characteristics including impact resistance.

  On the other hand, Patent Document 3 discloses a fiber reinforced resin composition using a block copolymer thermoplastic elastomer obtained from an aromatic vinyl compound such as styrene / butadiene / styrene block copolymer in a specific range and a conjugated diene. It is disclosed. With this technology, while impact resistance is improved, the elastic modulus is low, and high rigidity, which is a merit of using carbon fiber, is impaired. In addition, the heat resistance is low and further improvement is required to satisfy the practical characteristics.

International Publication No. 2010/119480 JP-A-2005-256206 JP 2014-105285 A

  The present invention has been made in view of such a current situation, and is reinforced with carbon fiber capable of obtaining a CFRP (molded product) having improved physical properties such as rigidity, bending characteristics and impact resistance while maintaining good moldability. A resin composition is provided.

  In order to solve the above problems, the present inventors have conducted intensive research, and in order to improve the physical properties of CFRP, it is indispensable to improve the adhesion between CF and the resin, but simply increasing the adhesion improves the strength but the impact resistance is insufficient. In order to improve the impact resistance, it is known to add rubber or the like. However, the addition of rubber certainly increases the impact resistance, but the rigidity that is characteristic of CFRP is impaired. At the same time as finding that the strength decreases because it hinders the effect of the adhesion improver, it is possible to achieve both rigidity, strength and impact resistance by using in combination with a specific impact resistance improver and adhesion improver The present invention was completed.

That is, the present invention is a carbon fiber reinforced resin composition having carbon fiber, polyolefin resin, olefin soft resin component and adhesion imparting agent as essential components, wherein the olefin soft resin component has the following conditions:
(1) The melt mass flow rate (MFR) at 230 ° C. and 21.18 N is 5 to 150 g / 10 min, and (2) the morphology when mixed with the polyolefin resin is a polyolefin resin as a continuous phase, Forming a sea-island structure with a soft resin component as a dispersed phase and having an average length of the dispersed phase of 0.1 to 10 μm,
The carbon fiber reinforced resin composition is characterized in that the blending ratio of the carbon fiber is 10 to 50% by mass with respect to the total of the carbon fiber, polyolefin resin, olefin soft resin component, and adhesion-imparting agent. .

  The adhesiveness-imparting agent has an acid-modified polyolefin resin unit and an epoxy resin unit, wherein the acid-modified polyolefin resin unit and the epoxy resin unit are bonded with an ester structure, and a secondary hydroxyl group in the epoxy resin unit. A resin containing is suitable.

  As the polyolefin resin, polypropylene homopolymer is suitable.

The olefin-based soft component preferably has a flexural modulus at 23 ° C. of 100 to 1600 MPa.
And ethylene-propylene block copolymer and / or acid-modified polypropylene are suitable.

  When the polyolefin resin, the olefin soft resin component, and the adhesion imparting agent are (A), (B), and (C), respectively, the respective compounding ratios are (A), (B), and (C). (A) 0.1 to 97.5% by mass, (B) 2 to 75% by mass, and (C) 0.5 to 70% by mass, and (A) and (B). And it is more preferable that they are (A) 40-90 mass%, (B) 2-49 mass%, and (C) 1-20 mass% with respect to the sum total of (C).

  Moreover, this invention is a molding of said carbon fiber reinforced resin composition.

  According to the present invention, it is possible to obtain a carbon fiber reinforced resin composition capable of obtaining CFRP having improved physical properties such as rigidity, bending characteristics and impact resistance. Therefore, the molded product obtained from the carbon fiber reinforced resin composition of the present invention can be suitably used for automobile parts, motorcycle / bicycle parts, etc., particularly parts requiring rigidity and impact resistance.

It is the figure which represented typically the morphology of the mixture of polyolefin resin and an olefin soft resin component. It is an AFM image of a mixture of a polyolefin-based resin and an olefin-based soft resin component.

Hereinafter, the present invention will be described in detail.
In the present specification, the polyolefin resin is also referred to as component (A), the olefin soft resin component as component (B), the adhesion-imparting agent as component (C), and the carbon fiber as component (D). A mixture containing the components (A), (B) and (C) and not containing the component (D) is also referred to as a polyolefin resin composition, and (D) is added to the mixture (A), (B), (C). And the mixture of (D) component is also called a carbon fiber reinforced resin composition.

  The components (A), (B), (C), and (D) will be described in this order. In the following, only representative compounds are described avoiding many complicated examples, and the present invention is not construed as being limited to these compounds or materials.

First, the polyolefin resin as the component (A) will be described.
The polyolefin resin is a resin obtained from a simple monomer containing an olefin such as ethylene or propylene, and an unmodified type which is not subjected to modification such as acid modification or reaction such as heterophasic copolymerization is suitable.

Specific examples of the olefin as the monomer include ethylene, propylene, 1-butene, 2-methyl-1-propene, 1-pentene, 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- Examples thereof include 1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, and 1-octene.
A homopolymer obtained by polymerizing only one kind of these olefins (homopolymer) may be used, or a copolymer obtained by copolymerizing two or more kinds (copolymer) may be used. Examples of copolymers include binary copolymers such as ethylene-propylene copolymer, propylene-butene copolymer, propylene-pentene copolymer, propylene-hexene copolymer, propylene-octene copolymer. And terpolymers such as ethylene-propylene-butene copolymer and ethylene-propylene-hexene copolymer. Among these, a propylene homopolymer which is a homopolymer of propylene is particularly preferable.

  The propylene homopolymer is said to have a good flexural modulus, which is an index of rigidity when the polyolefin resin composition of the present invention maintains appropriate fluidity and exhibits good moldability, and the polyolefin resin composition is a molded product. effective.

  Propylene homopolymer can be produced by slurry polymerization, gas phase polymerization or liquid phase bulk polymerization of propylene and the like using a polymerization catalyst. As a polymerization method for producing such a propylene polymer, batch polymerization and continuous polymerization are possible. Either method can be used.

  In addition, the catalyst used in order to obtain a propylene homopolymer is not specifically limited, A well-known catalyst can be used. For example, a so-called Ziegler-Natta catalyst or metallocene catalyst in which a titanium compound and organoaluminum are combined can be used. Of these, Ziegler-Natta catalysts are preferred.

  By using a Ziegler-Natta catalyst, the polymer can have high stereoregularity and a relatively high molecular weight can be obtained. Therefore, a propylene homopolymer suitable in terms of rigidity, heat resistance (melting point), and strength necessary for structural material applications can be obtained.

  Such a propylene homopolymer can be used by appropriately selecting a commercially available product. Commercially available products include Prime Polypro J105G, J106G, J106MG, J108M, J-700GP (manufactured by Prime Polymer Co., Ltd.), Novatec MA3 MA3H MA1B, SA08 (manufactured by Nippon Polypro Co., Ltd.), PM600A, PM600D, PM801A, PM802A, PM900A, PM900C, PL400A, PL500A, PL801C, PLA00A, PLB00A, PS412M, VS200A, PC412A, PC600A, PC600S, PF600R, HPA03A (manufactured by Sun Aroma Co., Ltd.), and the like.

Although the range of MFR of the polyolefin resin used in the present invention is not particularly limited, a range of 5 to 150 g / 10 min is preferable. If the MFR is lower than 5 g / 10 min, not only the fluidity is bad and the moldability is deteriorated, but if the fluidity is poor, for example, excessive stress is applied to the fiber at the time of compounding with the carbon fiber, thereby causing fiber breakage. There is a risk of deterioration of physical properties when a carbon fiber reinforced composite material is used. On the other hand, if the MFR is higher than 150 g / min, the fluidity is too good, so that not only the resin sagging may occur during melt processing and the appearance may deteriorate, but for example, the fiber concentration may be constant when compounded with carbon fiber. Otherwise, the strength may vary.
In this specification, the measurement conditions for MFR are the same as the measurement conditions for component (B) unless otherwise specified.

  Next, the olefin-based soft resin component (B) will be described. The olefin-based soft resin component functions as an impact resistance improver.

The olefin-based soft resin component is a resin obtained by polymerizing a monomer containing olefins as a main component, and includes olefin units in the monomer units constituting the resin. Here, the term “soft” refers to a property that is more ductile and softer and more elastic than inorganic materials such as glass and carbon. And it is preferable that it is softer or impact-resistant than (A) component.
Specific examples of the olefin constituting the olefin-based soft resin component include ethylene, propylene, 1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene, and 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, 1-octene and the like.

  A homopolymer obtained by polymerizing only one kind of these compounds or a copolymer obtained by polymerizing two or more kinds may be used, but a modified type in which a modification such as acid modification or a reaction such as heterophasic copolymerization is performed. Is suitable. And it is preferable that it is a thermoplastic resin which contains at least propylene in a monomer unit. The heterophasic copolymer refers to a special copolymer produced using a multistage reaction vessel in the process of producing a polyolefin-based resin, and the heterophasic copolymer produced thereby is an ordinary copolymer. Treat as different. For example, an ethylene-propylene block copolymer (block PP) is a heterophasic copolymer (heterophasic copolymer) and is treated as a copolymer different from a normal ethylene-propylene copolymer (copolymer). The block PP becomes the component (B), and the usual copolymer becomes the component (A).

  When propylene is not included in the monomer unit, the compatibility with the polyolefin resin is reduced when the polyolefin resin composition is used, and as a molded product of the polyolefin resin composition, when this is loaded, The interface between the continuous phase and the dispersed phase easily breaks down and the physical properties such as strength may be lowered, or the compatibility with the adhesion imparting agent becomes too good, and the function of the adhesion imparting agent is expressed. The physical properties such as strength when the polyolefin resin composition is molded may be insufficient. On the other hand, when propylene is contained in the monomer unit, both the polyolefin resin and the adhesion-imparting agent can maintain appropriate compatibility or incompatibility.

  The olefin-based soft resin component is preferably a thermoplastic resin that easily undergoes plastic deformation when heated. For example, in the case of a network polymer having poor thermoplasticity, the fluidity is insufficient, the molding processability is deteriorated, and the production efficiency is lowered.

  Furthermore, the olefin-based soft resin component is preferably block PP and / or acid-modified PP. These resin components are not only suitable for compatibility with the above-mentioned other components, but also can achieve a relatively high level of mechanical properties such as rigidity and impact resistance.

  In the case of acid-modified PP, the polypropylene is preferably a polypropylene modified with an unsaturated carboxylic acid or a derivative thereof, and has a carboxyl group or a carboxylic anhydride group in the polypropylene. In the case of modifying with an unsaturated carboxylic acid, the unsaturated bond reacts with polypropylene, whereby an acid-modified PP in which a carboxyl group or a carboxylic anhydride group is bound to polypropylene is obtained.

  Examples of the unsaturated carboxylic acid used for acid-modifying polypropylene include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, angelic acid, etc. Of unsaturated carboxylic acids. In addition, examples of the unsaturated carboxylic acid derivative include acid anhydrides, and examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, and nadic anhydride. Among these, unsaturated dicarboxylic acid and its derivative are preferable, and maleic anhydride is particularly preferable.

  The olefin-based soft resin component has a flexural modulus at 23 ° C. of 100 to 1600 MPa. If the flexural modulus is too lower than 100 MPa, the dimensional stability at a high temperature when the polyolefin-based resin composition is used may be lowered when it is used as a carbon fiber reinforced composite material and its molded product, whereas it is too higher than 1600 MPa. These shock resistances may be insufficient. The mechanism of insufficient impact resistance is not clear, but it is hard and brittle. Therefore, it is considered that the function of absorbing energy is reduced by plastic deformation of the olefin-based soft resin component when an impact load is applied.

  The olefin-based soft resin component has an MFR of 5 to 150 g / 10 min when measured at 230 ° C. and 21.18 N (2.16 kg). A preferred range is 5.5 to 120 g / 10 min. If it is lower than 5 g / 10 min, the kneadability is poor, so that when the polyolefin resin composition is prepared, unevenness is likely to occur in the composition, and as a result, the quality stability when formed into a molded product may be lowered. On the other hand, if the MFR is higher than 150 g / min, the fluidity is good and the moldability is good, but the strength and the like of the molded product may decrease due to the low molecular weight.

The (B) component olefinic soft resin component has a morphology when mixed with the (A) component polyolefinic resin to form a sea-island structure with the polyolefinic resin as the sea and the olefinic soft resin component as the island, And the average length of a dispersed phase is 0.1-10 micrometers.
This sea-island structure means a structure in which a phase composed of a polyolefin-based resin forms a continuous phase, and a phase composed of an olefin-based soft resinous component is dispersed in the continuous phase to form a dispersed phase. Being a sea-island structure means that they are not completely compatible.

  Here, the morphology refers to the fine structure of the resin, such as an optical microscope, a scanning electron microscope (SEM), a scanning transmission electron microscope (STEM), a transmission electron microscope (TEM), or an atomic force. This can be confirmed by observing a cross section of a composition obtained by melting and mixing a polyolefin resin and an olefin soft resin component with a microscope (AFM), a scanning probe microscope (SPM), or the like. Specifically, the surface of the resin composition is smoothed using a microtome, and then the probe is set to have a radius of curvature of 10 nm, a spring constant of 42 N / mm using a BrukerAXS Dimension Icon SPM device. It is possible to set and scan a TESPA NCHV manufactured by Bruker in tapping mode. The sea-island structure is confirmed by the method described in the examples.

  The two-dimensional shape of the dispersed phase is not particularly limited, but representative examples include a circle, an ellipse, a bowl, a rod, a string, a needle, a square, and an indefinite shape. Among these, those which are dispersed in a shape having no sharp portion such as a circle or an ellipse are particularly preferable. The reason for this is that it is relatively isotropically distributed without excessive concentration of stress locally.

  The average length of the dispersed phase can be read from the phase difference image obtained by observation by the above method as it is or from an image in which the contrast of the phase difference is enhanced. The average length of the dispersed phase comprising the olefin-based soft resin component is calculated by measuring the length of 100 or more dispersed phases and arithmetically averaging the dispersed phase lengths. In the present invention, a value obtained by dividing the sum of the maximum length and the minimum length of a single dispersed phase by 2 is defined as the dispersed phase length of the dispersed phase. The maximum length and the minimum length of the dispersed phase are, for example, distances represented by reference numerals 121 and 122 in FIG.

  Moreover, the average length of the dispersed phase which consists of an olefin type soft resin component is 0.1-10 micrometers. If the average length is less than 0.1 μm, it is too small compared to the size of the crack edge that is generated and propagated in the process of breaking the polyolefin resin composition, so that the resistance to breakage is not exhibited and the impact resistance There is a risk that physical properties such as the above cannot be expressed. On the other hand, when it is larger than 10 μm, there is a risk that the rigidity of the polyolefin resin composition, the carbon fiber reinforced composite material, and the molded product thereof is lowered.

  Although the mechanism of the olefin-based soft resin component is not clear, it is considered that the effect of the present invention is expressed by the following mechanism. That is, when a load is applied to the polyolefin-based resin composition of the present invention, the olefin-based soft resin component itself absorbs energy accompanying plastic deformation, or is generated starting from the interface between the olefin-based soft resin component and the polyolefin-based resin. It is thought that physical properties such as impact resistance are expressed by absorbing energy in the process of inducing a craze. In addition, when forming a polyolefin-based resin composition by forming a morphology in which the balance of compatibility with the polyolefin-based resin is controlled in an appropriate range, it is possible to suppress the loss of mechanical properties such as rigidity as much as possible. .

  Such an olefin-based soft resin component can be appropriately selected from commercially available products. Such commercial products include Novatec BC6C, BC4BSW, BC3AD, BC3L, BC2E, BC03C, BC03B, BC03GS, BC05B, BC06C, BC08F, BC10HRF (manufactured by Nippon Polypro Co., Ltd.), Prime TPO R110MP, R110E, T310E, Company Prime Polymer), Prime Polypro BJS-MU, J704LB, J704UG, J705UG, J715M, J707G, J707EG, J830HV, J708UG, J709QG (manufactured by Prime Polymer Co., Ltd.), PM472W, PM671A, PM761A, PM70X8PM70X8X , PM970A, PM970W, PM972Z, PMA60Z, PMB60W, PMB60W, VMD81 Block PP such as PB170A, PB270A, VB170A, VB370A, W, PC480A, PC684S (manufactured by Sun Allomer Co., Ltd.), Modic P502, P553A, P565, P555, P664V (manufactured by Mitsubishi Chemical Corporation), OREVAC G 18720, 18722 , 18725, 18729, 18732, 18732P, 18750, 18751, CA100 (manufactured by Arkema Co., Ltd.), Toyotack PMA-H1000P, PMA-H1100P, PMA-F2, M-100, M-300, M-213 (Toyobo Co., Ltd.) Company-made), Rike Aid REO-070-1, MG-250P, MG-400P (manufactured by Riken Vitamin Co., Ltd.), Umex 100TS, 110TS, 1001, 1010 (Sanyo Chemical Industries) There are acid-modified PP of formula company Ltd.).

Next, the adhesion imparting agent of the component (C) will be described.
The adhesion imparting agent has an action of improving the adhesion between the resin and the fiber. Accordingly, any unit having a unit compatible with the polyolefin-based resin and a unit that improves the adhesion to the fiber, preferably a polar group-containing unit such as a hydroxyl group may be used. However, it is not an olefin-based soft resin component of component (B).

Preferably, the adhesion-imparting agent has a structure containing both a skeleton having compatibility with the polyolefin resin and an epoxy resin unit having an adhesion action in one molecule. For this reason, since an epoxy resin component can be arrange | positioned with sufficient dispersibility with respect to the nonpolar polyolefin-type resin normally said to be low compatibility, a uniformity is given to a resin composition. As a result, local breakage due to stress concentration can be reduced, contributing to stable and high mechanical strength.
More preferably, it has an acid-modified polyolefin resin unit and an epoxy resin unit, the acid-modified polyolefin resin unit and the epoxy resin unit are bonded with an ester structure, and a secondary hydroxyl group is contained in the epoxy resin unit. Resin.

Such a resin can be obtained from an acid-modified polyolefin resin and an epoxy resin.
The preferred modification content of the acid-modified polyolefin resin is the same as that for the above-mentioned acid-modified PP, and maleic anhydride is particularly preferred.

  The epoxy resin as one raw material is not particularly limited as long as it has an epoxy group, a polyfunctional epoxy resin containing two or more epoxy groups is preferable, and a bifunctional epoxy resin having a secondary hydroxyl group is particularly preferable. Examples include, but are not limited to, polyglycidyl ether compounds, polyglycidyl amine compounds, polyglycidyl ester compounds, alicyclic epoxy compounds, and other modified epoxy resins. These epoxy resins may be used alone, or two or more of the same type of epoxy resins may be used in combination, or different types of epoxy resins may be used in combination. The epoxy resin includes a high molecular weight epoxy resin called a phenoxy resin. Further, the skeleton of the phenoxy resin is not particularly limited, and various structures can be used, but the structure of the bisphenol A skeleton is preferable.

Examples of the polyglycidyl ether compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethylbisphenol F type epoxy resin, biphenol type epoxy resin, hydroquinone type epoxy resin, bisphenol fluorene type epoxy resin, and naphthalene diol type epoxy resin. Bisphenol S type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl ether type epoxy resin, resorcinol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alkyl novolac type epoxy resin, aromatic modified phenol novolak type epoxy resin, Bisphenol novolac epoxy resin, naphthol novolac epoxy resin, β-naphthol aralkyl Type epoxy resin, naphthalene diol aralkyl type epoxy resin, α-naphthol aralkyl type epoxy resin, biphenyl aralkyl phenol type epoxy resin, trihydroxyphenyl methane type epoxy resin, tetrahydroxyphenyl ethane type epoxy resin, dicyclopentadiene type epoxy resin, alkylene A glycol type epoxy resin, an aliphatic cyclic epoxy resin, etc. are mentioned.
Examples of the polyglycidylamine compound include diaminodiphenylmethane type epoxy resin, metaxylenediamine type epoxy resin, 1,3-bisaminomethylcyclohexane type epoxy resin, isocyanurate type epoxy resin, aniline type epoxy resin, hydantoin type epoxy resin, Examples include aminophenol type epoxy resins.
Examples of the polyglycidyl ester compound include dimer acid type epoxy resin, hexahydrophthalic acid type epoxy resin, trimellitic acid type epoxy resin, and the like.
Examples of the alicyclic epoxy compound include aliphatic cyclic epoxy resins such as Celoxide 2021 (manufactured by Daicel Chemical Industries, Ltd.).
Other modified epoxy resins include, for example, urethane-modified epoxy resins, oxazolidone ring-containing epoxy resins, epoxy-modified polybutadiene rubber derivatives, CTBN-modified epoxy resins, epoxy-modified polyester resins, epoxy-modified melamine resins, and polyvinyl arenepolyoxides (for example, divinylbenzene). Dioxide, trivinylnaphthalene trioxide, etc.), phosphorus-containing epoxy resins and the like.

  The acid-modified polyolefin resin unit and the epoxy resin unit are bonded with an ester structure and contain the secondary hydroxyl group in the epoxy resin unit. The ester structure is a bond unit derived from the carboxyl group or acid anhydride group of the acid-modified polyolefin resin and the epoxy group or hydroxy group of the epoxy resin, and the acid-modified polyolefin resin unit and the epoxy resin unit are parts related to the bond unit. It is understood to be a unit excluding. In addition, when an epoxy resin forms an ester structure, an epoxy group is ring-opened, but a site generated by ring-opening and not involved in the ester structure is included in the epoxy resin unit.

The presence of the ester bond in the reaction product can be confirmed by IR absorption spectrum measurement. Since there is usually no solvent that dissolves the reaction product, the IR absorption spectrum is measured by a reflection method after film formation. Therefore, although there is no quantification of the peak of the absorption spectrum, the presence or absence of an ester bond peak can be confirmed, so the presence of the ester structure is determined by this.
The ester bond can be confirmed by measuring the IR absorption spectrum and observing the absorption by C═O stretching at 1735 to 1750 cm ⁻¹ .
The presence or absence of the secondary hydroxyl group contained in the epoxy resin unit can be confirmed by measuring the IR absorption spectrum and observing the absorption due to OH stretching as a broad peak at 3200 to 3600 cm ⁻¹ .

  It is preferable that the adhesion-imparting agent has the above-mentioned structural unit, these are bonded by an ester structure, and the epoxy resin structural unit has a secondary hydroxyl group structure. What was obtained by the manufacturing method may be used. For example, it can be obtained by an addition reaction between an acid-modified polyolefin resin and an epoxy resin, but is not limited to this method.

Next, the carbon fiber of component (D) will be described.
As the carbon fiber, various conventionally known carbon fibers can be used, and commercially available ones can be suitably used. Examples thereof include PAN-based carbon fibers, pitch-based carbon fibers, rayon-based carbon fibers, cellulose-based carbon fibers, vapor-grown carbon fibers, and graphitized fibers thereof. The PAN-based carbon fiber is a carbon fiber using polyacrylonitrile fiber as a raw material, the pitch-based carbon fiber is a carbon fiber using petroleum tar or petroleum pitch as a raw material, and the cellulose-based carbon fiber is a viscose rayon or The carbon fiber is made from cellulose acetate or the like, and the vapor-grown carbon fiber is made from hydrocarbon or the like. There is no restriction | limiting in particular in the kind of carbon fiber used by this invention. Moreover, this carbon fiber is not only used alone, but a plurality of types may be mixed and used.

  The form of the carbon fiber is not particularly limited, and various forms can be suitably used. A tow form in which single fibers are converged, a chopped form in which the fiber bundle is cut to an arbitrary length, a milled form that is further finely divided than the chopped form, a cross form in which the fiber bundle is knitted fabric, Examples include a form in which the tow is opened and aligned in one direction and held with a weft auxiliary yarn, and a form in which short fiber carbon fibers are processed into a mat or nonwoven fabric. From the viewpoint of processability when composited with a resin composition to obtain a carbon fiber reinforced resin composition, various carbon fiber raw materials in a suitable form are used depending on the processing method. On the other hand, from the viewpoint of strength development when a carbon fiber reinforced resin composition is molded into a molded product, a raw material having a long fiber length is preferable, and a tow form is particularly preferable.

The fiber diameter of the carbon fiber is not particularly limited, but any carbon fiber having a commercially available diameter can be suitably used. The diameter of carbon fibers that are usually marketed depends greatly on the diameter of the raw yarn, such as polyacrylonitrile for PAN-based carbon fibers and mesophase pitch for pitch-based carbon fibers. A suitable range of the fiber diameter is about 3 to 30 μm, preferably 5 to 20 μm. If the fiber diameter is too small, the carbon fiber may be easily damaged during manufacture, and the production may be difficult, or the carbon fiber may be easily damaged, and the productivity of the reinforcing fiber bundle may be reduced. In addition, when continuously producing pellets, a large number of carbon fibers must be bundled, which necessitates troublesome work of linking the fiber bundles, which may reduce productivity. On the other hand, if the fiber diameter is too large, the aspect ratio (average fiber length / average fiber diameter) of the carbon fiber when the carbon fiber reinforced resin composition is molded into a molded product is lowered, and the reinforcing effect is sufficiently exhibited. There is a risk of disappearing.
Here, the fiber diameter means an average diameter averaged by the number of monofilaments constituting the fiber bundle. The monofilament diameter is an average value of the longitudinal direction and the short direction of the cross section obtained when the monofilament is cut in the direction perpendicular to the fiber axis direction.
Moreover, the cross-sectional shape in the circumferential direction of the carbon fiber is not particularly limited. It may be a perfect circle or an ellipse, and may have a so-called kidney cross-sectional shape in which two of them are combined. Further, it may be a wavy shape having irregularities in the circumferential portion. The unevenness may be about 10% or less with respect to the monofilament diameter. Examples of the carbon fiber having an uneven shape on the surface in the circumferential direction include TR50S (manufactured by Mitsubishi Chemical Corporation).

The fiber length of the carbon fiber is not particularly limited, but basically, it is preferably as long as possible from the viewpoint of expressing the strength of the molded product when it is molded, for example, a fiber length of 0.1 mm or more. preferable. However, on the other hand, when monofilaments or carbon fiber bundles having a length greatly exceeding the dimensions of the carbon fiber reinforced resin composition are present in a twisted form in the carbon fiber reinforced resin composition, secondary processing such as molding is performed. May be difficult, and is not preferable. Therefore, although the length of the carbon fiber reinforced resin composition is not more than twice the longest distance, it is one guideline for the upper limit of the fiber length, but this does not particularly set the upper limit. .
Here, the fiber length is an average fiber length obtained by arbitrarily extracting 100 or more fibers contained in the carbon fiber reinforced resin composition and measuring the length. The dimension of a carbon fiber reinforced resin composition means the dimension of a pellet, when this is a pellet form.

  The aspect ratio of the carbon fiber is not particularly limited, but is preferably about 5 to 6000. If the aspect ratio is too small, the strength decreases, and if it is too large, the moldability may decrease.

The surface of the carbon fiber is preferably subjected to surface treatment by oxidation etching or coating. Oxidation etching treatment includes air oxidation treatment, oxygen treatment, treatment with oxidizing gas, treatment with ozone, corona treatment, flame treatment, (atmospheric pressure) plasma treatment, oxidizing liquid (nitric acid, alkali metal hypochlorite) Aqueous solution, potassium dichromate-sulfuric acid, potassium permanganate-sulfuric acid) and the like. Examples of the substance that covers the carbon fiber include carbon (graphene and the like), silicon carbide, silicon dioxide, silicon, plasma monomer, ferrocene, iron trichloride, and the like.
On the other hand, as a surface treatment such as coating, so-called sizing treatment can be mentioned. For the purpose of improving adhesiveness, convergence, and wettability, various epoxy compounds described later may be treated by combining one or more kinds. Further, if necessary, a sizing agent such as urethane, olefin, acrylic, nylon, butadiene, or epoxy may be used.

  Next, the blending ratio of each component with respect to the total of the essential components (A) to (C), that is, the blending ratio of the polyolefin-based resin, the olefin-based soft resin component, and the adhesion imparting agent will be described.

  The blending ratio of the polyolefin resin is preferably 0.1 to 97.5% by mass, preferably 5 to 95% by mass, and more preferably 10 to 90% by mass. Since general-purpose commercial products can be used as the polyolefin-based resin, the higher the compounding ratio, the more advantageous in terms of cost, more preferably 40% by mass or more, 50% by mass or more, and preferably 60% by mass or more. More preferably. However, when there are few compounding ratios of an olefin type soft resin component and adhesiveness imparting agent, the effect of the present invention cannot be obtained suitably.

  The blending ratio of the olefin-based soft resin component is preferably 2 to 75% by mass, more preferably 5 to 70% by mass, further preferably 10 to 65% by mass, and most preferably 2 to 49% by mass. . If it is less than 2% by mass, the presence frequency of the dispersed phase in the polyolefin-based resin composition is too low, and the probability that the dispersed phase is present at a place where a load is applied when locally loaded is not stable. This is not preferable because there is a possibility that the evaluation result of the mechanical properties when formed into a molded product may cause variations. On the other hand, when it is more than 75% by mass, there is a risk of lowering rigidity when formed into a molded product.

The blending ratio of the adhesion-imparting agent is preferably 0.5 to 70% by mass, more preferably 1 to 50% by mass, still more preferably 1 to 20% by mass, or 2 to 30% by mass. If the amount is less than 0.5% by mass, the carbon fiber and the polyolefin resin composition when the carbon fiber reinforced composite material is used cannot be firmly adhered, and the mechanical properties such as strength may not be satisfied. On the other hand, when the amount is more than 70% by mass, the interaction with the carbon fiber is too strong. Conceivable.
In terms of cost, the component (A) is the main component, the component (B) is less than 50% by mass, preferably 2% by mass or more and less than 30% by mass, and the component (C) is less than 10% by mass, preferably It is advantageous that the content be 2% by mass or more and less than 10% by mass.

  In addition, since the polymer blend consisting of the polyolefin resin and the olefin soft resin component is phase-separated and the conditions for forming the sea-island structure are different depending on the type of the polyolefin resin, the type of the olefin soft resin component and the combination thereof, Even if the olefin-based soft resin component does not satisfy the above condition (3), the effect of the present invention can be obtained if the condition (3) is satisfied during actual blending.

  Component (D), that is, the blending ratio of carbon fibers, is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and still more preferably based on the total of components (A) to (D). Is 20-40 mass%. If it is less than 10% by mass, the effect of reinforcing the resin by carbon fiber does not appear, and if it exceeds 50% by mass, the toughness may be lost.

The carbon fiber reinforced resin composition of the present invention can be divided into a resin component (polyolefin resin composition) and carbon fiber.
The MFR of the polyolefin resin composition is not particularly limited, but is preferably 50 to 100 g / 10 min. If it is lower than 50 g / min, the molding processability of the polyolefin-based resin composition itself deteriorates. For example, when it is formed into a molded product, there is a possibility that it may lead to a short shot or a decrease in weld strength. In addition, when the carbon fiber reinforced composite material is used, since the impregnation property of the resin into the carbon fiber is too low, the production method and production conditions are remarkably limited. On the other hand, if it is higher than 100 g / min, for example, burrs are produced when formed into a molded body, which may lead to deterioration in appearance quality.

  In addition to the essential components, polyolefin resin compositions include various thermoplastic resins and additives such as dispersants, lubricants, plasticizers, flame retardants, antioxidants (phenolic antioxidants, phosphorus Antioxidants, sulfur-based antioxidants), antistatic agents, light stabilizers, ultraviolet absorbers, crystallization accelerators (nucleating agents), foaming agents, crosslinking agents, antibacterial and other modifying additives, pigments Colorants such as dyes, carbon black, titanium oxide, bengara, azo pigments, anthraquinone pigments, particulate fillers such as phthalocyanine, talc, calcium carbonate, mica, clay, short fiber fillers such as wollastonite, titanium Whiskers such as potassium acid can be added. These additives may be added during pellet production and contained in the pellet, or may be added when a molded body is produced from the pellet.

  In addition, in the case of a carbon fiber reinforced composite material and a molded body thereof, a diluent made of a thermoplastic resin such as a polypropylene resin same as the polyolefin resin composition can be blended in order to adjust the composition ratio. . A dry blend method can be used for blending with the diluent. In order to maintain the fiber length in the composition and obtain an effect of improving higher rigidity, impact resistance, and durability, it is preferable to apply the dry blend method when producing a molded body.

Next, the manufacturing method of the carbon fiber reinforced resin composition of this invention is demonstrated.
Although it does not specifically limit about the manufacturing method of the carbon fiber reinforced resin composition of this invention, A conventionally well-known method can be used suitably. Carbon fiber is impregnated and compounded with carbon fiber such as tow form in which single fibers are converged, chopped form in which the fiber bundle is cut to an arbitrary length, milled form in which the fiber bundle is further finely divided. Manufacturing method to make so-called carbon fiber reinforced pellets that can be extruded / injection molded, a form of cloth in which the fiber bundle is knitted woven, a form in which the tow is opened and aligned in one direction and held with a weft auxiliary yarn , A manufacturing method of a so-called prepreg sheet / stampable sheet that can be press-molded by impregnating a resin into a carbon fiber in a form obtained by processing short fiber carbon fiber into a mat or non-woven fabric, and the like. It is done. Carbon fiber reinforced pellets are preferable from the viewpoint of achieving both moldability and strength development, and so-called long fiber reinforced pellets made of carbon fiber reinforced pellets using tow are particularly preferable.

When the carbon fiber reinforced resin composition of the present invention is obtained as a short fiber reinforced resin pellet, it can be produced by melt-kneading a part or all of the above components (A) to (D) in an extruder or the like, When it is a long fiber reinforced resin pellet, it can be produced by a known method such as a drawing method. A part of the components (A) to (D) may be separately melt-kneaded and then mixed (blended).
The deformation of the fiber reinforced resin pellet may be in the form of powder or flakes.

  The long fiber reinforced resin pellet has a larger aspect ratio of the fibers in the composition, and it is easy to obtain a composition having high strength. The pellet length of the long fiber reinforced resin pellet is usually 2 to 200 mm, and those having a length of about 10 to 30 mm are commercially available, and these can be suitably used. The longer the pellet length, the longer the fiber length contained in the pellet, which is preferable from the viewpoint of strength development. If it is too long, molding may be difficult, but any molding method that ensures moldability may be used, and no upper limit is required. If the pellet length is too short, the effect of improving rigidity, heat resistance and mechanical properties is low, and warping deformation may be increased. The pellet length is not particularly limited, but is preferably 10 mm or more, more preferably 12 mm or more, and further preferably 15 mm or more. The carbon fibers in the pellet are preferably arranged in a state parallel to each other in a direction horizontal to the longitudinal direction of the pellet because the fiber length is longer.

  For long fiber reinforced resin pellets, roving of thousands of reinforcing fibers is guided to an impregnation die, uniformly impregnated with molten resin between the filaments, and then cut to the required length (for example, 2 to 200 mm). Can be obtained more easily. For example, a molten resin containing the above components (A) to (C) is supplied from an extruder into an impregnation die provided at the tip of the extruder, while passing a continuous fiber bundle, and the molten resin is passed through this fiber bundle. After impregnation, pull through the nozzle and pelletize to the required length. It is also possible to adopt a method in which the components (A) to (C) are dry blended, put into a hopper of an extruder, and supplied while simultaneously performing melt mixing or modification.

  The method for impregnating the carbon fiber with the molten resin is not particularly limited, and the method is a method in which the reinforcing fiber roving is passed through the resin powder fluidized bed and then heated to the melting point of the resin (Japanese Patent Publication No. 52-3985). A method of impregnating a reinforcing fiber roving with a molten resin using a crosshead die (Japanese Patent Laid-Open Nos. 62-60625, 63-1332036, 63-264326, 1 No. 208118), a method in which resin fibers and rovings of reinforcing fibers are mixed and then heated above the melting point of the resin to impregnate the resin (Japanese Patent Laid-Open No. Sho 61-118235), a plurality of rods inside the die A method in which a roving is wound around in a zigzag manner to open the fiber and impregnated with a molten resin (Japanese Patent Laid-Open No. 10-264152). The method of passing (WO97 / 19805 discloses), etc., any method can be used.

In the process of melting the resin, an extruder with two or more feed parts is used. From the top feed, additives such as resin and organic peroxide decomposition agents are added, and another resin is fed from the side feed. May be. By adding a resin decomposing agent, the polyolefin resin can be slightly decomposed to reduce the molecular weight and improve the impregnation property.
Two or more extruders (extrusion sections) may be used, and one or more of the extruders may be charged with a resin and a resin decomposer. Further, a resin and a resin decomposing agent may be put into at least one place of the extruder.

  The short fiber reinforced resin pellet can be produced by kneading and dispersing each component in a predetermined ratio with a roll mill, a Banbury mixer, a kneader or the like. You may dry blend with a tumbler type blender, a Henschel mixer, a ribbon mixer, etc. The mixture is kneaded with a single screw extruder, twin screw extruder or the like to form a pellet-shaped molding material.

A molded product can be obtained by molding the carbon fiber reinforced resin composition of the present invention.
As a method for molding the molded product of the present invention, known molding methods such as injection molding, extrusion molding, hollow molding, compression molding, injection compression molding, gas injection molding, foam injection molding, and the like are used. Applicable without any restrictions. In particular, an injection molding method, a compression molding method, and an injection compression molding method are preferable. The molding temperature is generally preferably 150 to 250 ° C, more preferably 160 to 220 ° C. Therefore, as the resin component, a material showing an appropriate melt viscosity in such a molding temperature range is selected.

  In order to adjust the composition ratio, the fiber reinforced resin pellet that is the carbon fiber reinforced resin composition of the present invention can be mixed with a diluent made of the same thermoplastic resin as the fiber reinforced resin pellet. . A dry blend method can be used for blending with the diluent. In order to maintain the fiber length in the composition and to obtain higher rigidity, impact resistance, and durability improvement effects, after dry blending, do not pass through an extruder and use it directly in a molding machine such as an injection molding machine. Is preferred. The blending ratio of the diluent is determined by the reinforcing fiber content of the fiber reinforced resin group pellet and the reinforcing fiber content required for the final molded product, but from the viewpoint of the effect of improving rigidity, impact resistance, and durability, Usually, the range of 10-40 mass% is preferable.

  If the average fiber length of the carbon fibers present after molding is too short, it is difficult to obtain improvement effects such as rigidity, strength, impact resistance, etc., and 0.1 mm or more is preferable. From the standpoint of strength development, the longer the length, the better. However, when carbon fibers with a length that greatly exceeds the size of the molded product are present in a meandering shape or innumerable crossing in the molded product, voids are easily formed between the carbon fibers, and a resin is formed in the molded product. There is a high probability that void regions that are not impregnated, that is, so-called voids, are generated, leading to a decrease in strength. Accordingly, a length within twice the longest distance among the dimensions of the molded product is one guideline for the upper limit of the fiber length, but this does not set an upper limit in particular.

  Next, a method for producing a polyolefin resin composition used in the carbon fiber reinforced resin composition of the present invention will be described.

  The method for producing the polyolefin resin composition used in the carbon fiber reinforced resin composition of the present invention is not particularly limited, but it is a so-called polymer alloy that forms a blend polymer by chemically bonding two or more kinds of polymers. A manufacturing method can be used suitably. Particularly preferred is a method in which each component is uniformly mixed and reacted. For example, a known melt kneader such as a single or twin screw extruder, a Banbury mixer, a kneader, or a mixing roll can be used.

  Although mixing temperature is not specifically limited, it is 150-250 degreeC, Preferably it is 160-240 degreeC, More preferably, it is 165-235 degreeC. A temperature that is 15 to 20 ° C. higher than the melting point of the polyolefin resin is particularly preferable. When the mixing temperature is less than 150 ° C., the polyolefin resin does not melt, and there is a possibility that it cannot be uniformly melt-mixed. On the other hand, when the mixing temperature exceeds 250 ° C., the molecular weight is reduced due to the cleavage of the molecular chain, which may cause a reduction in strength when formed into a molded product.

  The mixing time is not particularly limited, but in the case of normal melt kneading, it may be about 1 to 30 minutes. Although it depends on the mixing temperature, if it is too short, the time from the dissolution or melting of each component is too short, so the system may not reach a uniform state. There is a risk of becoming. On the other hand, depending on the mixing temperature, if it is too long, each component may cause degradation such as decomposition. Due to the decrease in molecular weight, the mechanical strength of the molded product may be reduced, and the formation of by-products increases the number of crosslinking points in the molecular chain structure. There is a risk of worsening.

  EXAMPLES The present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these. Unless otherwise specified, parts represent parts by mass, and% represents mass%. Various physical properties were measured by the following methods.

(1) MFR:
Based on JIS K 7210-1999, the measurement was performed under conditions of a temperature of 230 ° C. and a load of 2.16 kg.
(2) Tensile yield strength, tensile fracture strength, tensile modulus, tensile fracture strain:
A universal material testing machine (Instron, Model 5582) was used. At room temperature, a dumbbell test piece having a length of 215 mm including the grip part, a width of 10 mm, and a thickness of 4 mm was measured with a chuck distance of 114 mm and a speed of 50 mm / min. A tensile test was conducted, and the tensile yield strength, tensile fracture strength, tensile elastic modulus, and tensile fracture strain were determined from the obtained stress-strain diagram.
(3) Flexural strength, flexural modulus:
A fully automatic bending tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., bend graph tester) was used. At room temperature, a rod-shaped test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was measured at a speed of 2 mm / min. A three-point bending test was performed, and bending strength and bending elastic modulus were obtained from the obtained stress-strain diagram.
(4) Impact strength:
A Charpy impact tester (manufactured by Yasuda Seiki Seisakusho, No. 258PC-S) was used. At room temperature, the Charpy impact test was performed with an impact test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm, having a V notch having a depth of 2 mm penetrating the plate thickness with the longitudinal direction of the test piece being the MD direction. Absorbed energy was determined from the difference in hammer potential energy before and after the test piece was broken, and the Charpy impact value was obtained.
(5) Absorbed energy:
A surface impact tester (manufactured by JT Toshi, IITM-18) was used. A test piece having a plate thickness of about 2.5 mm and a length and width of 70 mm at room temperature was used. A plate-like test piece was placed on a perforated support with a diameter of 40 mm, and a striker with a tip of R of 20 mm was dropped from a height of 1 m immediately above the center of the hole. After converting the load-displacement curve to the load-displacement curve using the formula described in JIS K 7211-2 from the load-time curve when the striker penetrates the plate-shaped test piece, the value obtained by integrating the load over the entire displacement section is tested. The absorbed energy required for breaking the piece was evaluated.
(6) Deflection temperature under load:
A load deflection temperature tester (No.148-HDPC-3, manufactured by Yasuda Seiki Seisakusho Co., Ltd.) was used. The temperature of the oil tank is set to 120 ° C./min. With a bending stress applied to a multipurpose test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm with a span of 64 mm. The temperature when the temperature was increased at a speed of and the specified deflection amount (0.34 mm) was reached was defined as the deflection temperature under load.

  The abbreviations and physical property values of the materials used are shown below.

(Polyolefin resin)
A-1: Polypropylene homopolymer (Nippon Polypro Co., Ltd., SA08, MFR 85 g / 10 min)
(Olefin soft resin component)
B-1: Block PP (Nippon Polypro Co., Ltd., BC10HRF, flexural modulus 1100 MPa, MFR 111 g / 10 min)
B-2: Maleic anhydride-modified PP (Mitsubishi Chemical Corporation, Modic P565, flexural modulus 600 MPa, MFR 5.7 g / 10 min)
B-3: Maleic anhydride-modified PP (manufactured by Mitsubishi Chemical Corporation, Modic P555, flexural modulus 1200 MPa, MFR 6.2 g / 10 min)
B-4: Hydrogenated styrene-based thermoplastic elastomer (Asahi Kasei Corporation, Tuftec H1062, flexural modulus 26 MPa, MFR 4.5 g / 10 min)

(Other)
PMA-H1000P: maleic anhydride modified PP (manufactured by Toyobo Co., Ltd., PMA-H1000P flexural modulus 1400 MPa, MFR 200 g / 10 min or more)
YP-70: BPA / BPF copolymer type phenoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., phenotote YP-70)
2E4MZ-A: Imidazole-based catalyst (manufactured by Shikoku Kasei Kogyo Co., Ltd., Curesol 2E4MZ-A)

(Morphology)
A mixture obtained by dry blending 20 parts of olefin-based soft resin component (B-1 to B-4) and 80 parts of polyolefin-based resin A-1 was added to a twin-screw kneading extruder (manufactured by Nippon Steel Works, TEM26SS). After charging, melt mixing was performed at 200 ° C. The strand discharged from the die port at the tip of the barrel was cooled in a water tank, then cut into a length of about 3 mm with a pelletizer, and further allowed to cool to obtain a pellet of a mixture of an olefin soft resin component and a polyolefin resin. The obtained pellets were injection molded at a cylinder temperature of 230 ° C. and a mold temperature of 40 ° C. using an injection molding machine (manufactured by Nippon Steel Works, J180AD) to obtain a molded product. The surface of the obtained molded product was smoothed using a microtome to obtain test pieces for morphological observation and for measuring the dispersed phase length. The obtained test piece was observed at 23 ° C. using a Dimension Icon type SPM device manufactured by Bruker AXS. The probe was set with a Bruker TESPA NCHV having a tip radius of curvature of 10 nm and a spring constant of 42 N / m, and scanned in a tapping mode for observation. The length of 100 dispersed phases was measured from the phase image obtained as a result of observation, and the average length was calculated by arithmetically averaging the lengths of the dispersed phases. The results are shown in Table 1.
Here, it demonstrates with FIG. 1 which represented the morphology typically. 100 is a sea-island structure, 110 is a continuous phase, and 120 is a dispersed phase. The maximum length and the minimum length of the dispersed phase are distances represented by 121 and 122, respectively.

Synthesis example 1
Two parts were prepared by dry blending 70 parts of PMA-H1000P, 30 parts of YP-70 and 1 part of 2E4MZ-A to obtain a mixture, and then preheating the inside of the barrel to 170 to 200 ° C. The mixture was put into a kneading extruder (above) and melt mixed. After completion of the melt mixing, the strand discharged from the die port at the tip of the barrel was cooled in a water tank, cut into a length of about 3 mm with a pelletizer, and further allowed to cool to obtain an adhesion-imparting agent C-1. It was confirmed by FT-IR that there was a peak derived from the ester bond of the obtained adhesion-imparting agent and a peak derived from the secondary hydroxyl group of the epoxy resin as the raw material of the adhesion-imparting agent.

Reference example 1
72 parts of A-1 as a polyolefin resin, 23 parts of B-1 as an olefin soft resin component, and 5 parts of C-1 as an adhesion-imparting agent were dry blended to obtain a mixture, and then the mixture was used to synthesize The same operation as in Example 1 was performed to obtain a composition P1.

Reference Examples 2 to 10
Except having changed into the compounding ratio shown in Table 2, operation similar to Example 1 was performed and composition P2-P10 was obtained.

Comparative Reference Examples 1-6
Except having changed into the compounding ratio shown in Table 3, operation similar to the reference example 1 was performed, and composition HP1-HP6 was obtained.

Example 1
70 parts of the composition P1 as a polyolefin-based resin composition is supplied from a main hopper to a twin-screw kneading extruder (described above) that has been preheated to 170 to 230 ° C. in the barrel in advance, and then the downstream side Carbon fiber (manufactured by Mitsubishi Chemical Corporation, chopped fiber, φ7 μm, 3 mm length) was supplied from the hopper so as to be 30 parts, and melt mixing was performed. After the strand discharged from the die port at the tip of the barrel was cooled in a water tank, it was cut into a length of about 3 mm with a pelletizer and further allowed to cool to obtain pellets of a carbon fiber-containing polyolefin resin composition. The obtained pellets were injection-molded using an injection molding machine (above) at a cylinder temperature of 230 ° C., a mold temperature of 40 ° C., and a back pressure of 15 MPa to obtain a molded product. Table 4 shows the mechanical properties of the obtained molded product.

Examples 2-10
Except having changed into the composition shown in Table 4, operation similar to Example 1 was performed and the molding was obtained. Table 4 shows the mechanical properties of the obtained molded product.

Comparative Examples 1-6
Except having changed into the composition shown in Table 5, operation similar to Example 1 was performed and the molding was obtained. Table 5 shows the mechanical properties of the obtained molded product.

Reference Examples 11-13 and Comparative Reference Example 7
Except having changed into the compounding ratio shown in Table 6, operation similar to the reference example 1 was performed, and the compositions P11-P13 and HP7 were obtained.

Example 11
60 parts of the composition P11 as a polyolefin-based resin composition is supplied from a main hopper to a twin-screw kneading extruder (above) that has been preheated to 170 to 230 ° C. in the barrel in advance, and then the downstream side Carbon fiber (manufactured by Mitsubishi Chemical, chopped fiber, φ7 μm, 6 mm length) was supplied from the hopper so as to be 40 parts, and melt mixing was performed. After the strand discharged from the die port at the tip of the barrel was cooled in a water tank, it was cut into a length of about 3 mm with a pelletizer and further allowed to cool to obtain a pellet CP11 of a carbon fiber reinforced resin composition.

Comparative Examples 7-8
Except for using the HP1 and HP7 obtained in Comparative Reference Examples 1 and 7 as the polyolefin resin composition, the same operation as in Example 11 was performed to obtain pellets HCP1 and HCP7 of the carbon fiber reinforced resin composition.

Example 12
After dry blending 75 parts of the pellet CP11 obtained in Example 11 and 25 parts of the composition P12 obtained in Reference Example 12 to obtain a mixture having a carbon fiber content of 30 parts by mass, Using an injection molding machine (manufactured by Nippon Steel Works, J220AD), a molded product was obtained by injection molding at a cylinder temperature of 230 ° C., a mold temperature of 40 ° C., and a back pressure of 3 MPa. Table 7 shows the composition ratios and mechanical properties of (A) to (C) after molding.

Example 13
Except having replaced the composition with the composition P13 obtained in Reference Example 13, the same operation as in Example 12 was performed to obtain a molded product. Table 7 shows the composition ratios and mechanical properties of (A) to (C) after molding.

Comparative Examples 9-10
Except that the pellets were replaced with HCP1 and HCP7 obtained in Comparative Examples 7 and 8, and the composition was replaced with the composition HP1 obtained in Comparative Reference Example 1, the same operation as in Example 12 was performed to obtain a molded product. It was. Table 7 shows the composition ratios and mechanical properties of (A) to (C) after molding.

  The molded product of the carbon fiber reinforced polyolefin resin composition using the polyolefin resin composition of the present invention has higher mechanical properties such as bending properties and impact resistance than when the polyolefin resin composition of the comparative example is used. You can see that both levels are compatible.

100 Sea-island structure 110 Continuous phase 120 Dispersed phase

Claims (8)

A carbon fiber reinforced resin composition comprising carbon fiber, polyolefin resin, olefin soft resin component and adhesion-imparting agent as essential components, wherein the olefin soft resin component has the following condition (1) 230 ° C., 21. A sea-island in which the melt mass flow rate in 18N is 5 to 150 g / 10 min, and (2) the morphology when mixed with the polyolefin-based resin is a polyolefin-based resin as a continuous phase and an olefin-based soft resin component as a dispersed phase. Forming a structure and having an average length of the dispersed phase of 0.1 to 10 μm,
The carbon fiber reinforced resin is characterized in that the blending ratio of the carbon fiber is 10 to 50% by mass with respect to the total of the carbon fiber, polyolefin resin, olefin soft resin component, and adhesion-imparting agent. Composition.   The adhesion imparting agent has an acid-modified polyolefin resin unit and an epoxy resin unit, the acid-modified polyolefin resin unit and the epoxy resin unit are bonded with an ester structure, and a secondary hydroxyl group is present in the epoxy resin unit. The carbon fiber reinforced resin composition according to claim 1, which is a contained resin.   The carbon fiber reinforced resin composition according to claim 1 or 2, wherein the polyolefin resin is a polypropylene homopolymer.   The carbon fiber reinforced resin composition according to any one of claims 1 to 3, wherein the flexural modulus at 23 ° C of the olefin-based soft component is 100 to 1600 MPa.   The carbon fiber reinforced resin composition according to any one of claims 1 to 4, wherein the olefin-based soft resin component is an ethylene-propylene block copolymer and / or an acid-modified polypropylene.   When the polyolefin resin, the olefin soft resin component, and the adhesion imparting agent are (A), (B), and (C), respectively, the respective compounding ratios are (A), (B), and (C). The total amount of (A) is 0.1 to 97.5% by mass, (B) is 2 to 75% by mass, and (C) is 0.5 to 70% by mass. The carbon fiber reinforced resin composition as described.   The said mixture ratio is (A) 40-90 mass%, (B) 2-49 mass%, and (C) 1-20 mass% with respect to the sum total of (A), (B), and (C). Item 7. A carbon fiber reinforced resin composition according to Item 6. The molded product of the carbon fiber reinforced resin composition according to any one of claims 1 to 7.

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