JP2017048314A - Composition and molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition capable of obtaining a molded body which is excellent adhesion between a fiber and a matrix resin, and is also excellent in mechanical strength such as impact resistance and bending strength.SOLUTION: A composition contains a conjugated diene-based polymer (A), a fiber (B), and a thermoplastic resin (C). The composition contains 10 pts.mass or more and 100 pts.mass or less of the fiber (B) with respect to 100 pts.mass of the thermoplastic resin (C). The conjugated diene-based polymer (A) has an amino group, and a fiber length of the fiber (B) is 3 mm or more and 50 mm or less.SELECTED DRAWING: None

Description

  The present invention relates to a composition containing fibers and a molded body obtained by molding the composition.

  A fiber reinforced resin (FRP) is a material in which reinforcing fibers such as glass fibers and carbon fibers are hardened with a resin, and is a composite material excellent in mechanical strength, heat resistance, moldability, and the like. Therefore, FRP is used as a material in a wide range of fields such as aviation, space use, vehicle use, building material use, and sports use.

  Among these, carbon fiber reinforced resin (CFRP) is characterized by lightness in addition to high strength. As resin, what reinforce | strengthened carbon fiber using the thermosetting epoxy resin is mainstream, for example, is employ | adopted as the structural material etc. of an aircraft. On the other hand, FRP using a thermoplastic resin has attracted attention in recent years because it has the characteristics that in addition to the above characteristics, the molding cycle can be shortened and can be recycled.

  In CFRP using such a thermoplastic resin, a fiber reinforced resin rod (strand) is obtained by impregnating the thermoplastic resin while aligning the long carbon fiber under tension, and then cutting it into an arbitrary length. It is performed to use carbon long fiber reinforced resin pellets obtained in this way (see, for example, Patent Document 1).

JP 05-112657 A

  However, the carbon long fiber reinforced resin pellets described above may have insufficient adhesion between the carbon fibers and the matrix resin, and may be insufficient in terms of improving mechanical properties such as bending strength. Therefore, when such a carbon long fiber reinforced resin pellet is subjected to a load such as a bending load, a crack may occur from the interface between the carbon fiber and the matrix resin. The cracks generated in this way propagate to the other interface between the carbon fiber and the matrix resin, thereby causing further cracks and finally traversing the molded body, leading to total destruction.

  Therefore, some aspects according to the present invention are excellent in adhesion between the fiber and the matrix resin, and in mechanical strength such as impact resistance and bending strength, by solving at least a part of the problems. Provided is a composition from which a molded body is obtained.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the composition according to the present invention is:
Containing a conjugated diene polymer (A), a fiber (B), and a thermoplastic resin (C);
Containing 10 to 100 parts by mass of the fiber (B) with respect to 100 parts by mass of the thermoplastic resin (C);
The conjugated diene polymer (A) has an amino group,
The fiber length of the said fiber (B) is 3 mm or more and 50 mm or less.

[Application Example 2]
In the composition of Application Example 1,
The content ratio of the conjugated diene polymer (A) may be 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin (C).

[Application Example 3]
In the composition of Application Example 1 or Application Example 2,
The fiber (B) may be a carbon fiber.

[Application Example 4]
In the composition of any one of Application Examples 1 to 3,
The thermoplastic resin (C) may be an olefin resin.

[Application Example 5]
One aspect of the molded body according to the present invention is:
It is obtained by molding the composition of any one of Application Examples 1 to 4.

  According to the composition of the present invention, it is possible to obtain a molded article having excellent adhesion between fibers and a matrix resin and excellent mechanical strength such as impact resistance and bending strength.

  Hereinafter, preferred embodiments according to the present invention will be described in detail. It should be understood that the present invention is not limited only to the following embodiments, and includes various modifications that are implemented within a scope that does not change the gist of the present invention.

  In the present specification, the conjugated diene polymer (A) is referred to as “component (A)”, the fiber (B) as “component (B)”, and the thermoplastic resin (C) as “component (C)”. It may be used for short.

1. Composition In general, when a load such as a bending load is applied to an FRP molded product, the adhesion between the fiber and the matrix resin tends to be insufficient, and cracks are likely to occur from the interface between the fiber and the matrix resin. The cracks generated in this manner propagate to the other interface between the fiber and the matrix resin, thereby further inducing cracks, and finally traversing the molded body, leading to total destruction.

  In order to suppress the occurrence of cracks due to such a mechanism, it is necessary to improve the adhesion at the interface between the fiber and the matrix resin. In order to achieve this, the composition according to this embodiment contains a conjugated diene polymer (A), fibers (B) having a fiber length of 3 mm to 50 mm, and a thermoplastic resin (C). The component (B) is contained in an amount of 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the component (C) which is a matrix resin, and the component (A) further has an amino group. Hereinafter, each component contained in the composition according to the present embodiment will be described.

1.1. Conjugated diene polymer (A)
The composition according to this embodiment includes a conjugated diene polymer (A). The component (A) includes the component (B) and the component (C) when a load such as a bending load is applied by firmly bonding the component (B) and the component (C) in the molded body according to the present embodiment. ) It is considered that cracking is suppressed from the interface of the component, and mechanical strength such as bending strength and falling weight impact strength of the molded body is improved.

The component (A) used in the present embodiment has an amino group. The method for imparting the amino group to the polymer is not particularly limited, and examples thereof include a method for obtaining the component (A) by polymerizing a monomer having an amino group. In this specification, “amino group” means a primary amino group (—NH ₂ ), a secondary amino group (—NHR, where R is a hydrocarbon group), and a tertiary amino group (—NRR ′, where R , R ′ represents any one of hydrocarbon groups), and the amino group may be protected by a protecting group.

  The amount of amino groups per molecular chain of component (A) is preferably 1 or more, more preferably 5 or more, and particularly preferably 10 or more. In order to prevent gelation of the polymer during production, the amount of amino groups per molecular chain is preferably 100 or less, more preferably 50 or less. (A) Although the determination method of the amount of amino groups in a component is not specifically limited, It can obtain | require by IR method, NMR method, an amine titration method, etc. When the amino group amount is in the above range, it is considered that the adhesion with the component (B) becomes stronger and the mechanical strength of the molded body obtained by molding the composition according to this embodiment is further improved.

  The weight average molecular weight (Mw) of the component (A) in terms of polystyrene in the gel permeation chromatography (GPC) method is preferably 30,000 to 2,000,000, more preferably 40,000 to 1,000,000, particularly preferably 50,000 to 50. It is ten thousand. In addition, the melt flow rate (MFR: 230 ° C., 2.16 kg) of component (A) measured according to JIS K7210 is preferably 0.1 to 100 g / 10 min, more preferably 0.2 to 50 g. / 10 min, particularly preferably 0.3 to 30 g / 10 min.

  The component (A) may be composed of only repeating units derived from conjugated dienes, but may have repeating units derived from monomers other than conjugated dienes as necessary. The component (A) may be a block type polymer in which the same monomer forms a repeating unit, and forms a random type polymer in which different monomers are randomly polymerized. Also good. In order to enhance the compatibility between the component (A) and the component (C) and adhere the component (B) and the component (C) more firmly, the component (A) is preferably a block copolymer. . In particular, from the viewpoint of improving the weather resistance and mechanical strength of the resulting molded article, the component (A) is preferably a hydrogenated polymer. Hereinafter, the conjugated diene polymer (A) will be described in detail.

1.1.1. Conjugated diene (A) A component contains the repeating unit derived from a conjugated diene. Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-octadiene, 1,3-hexadiene, 1, Examples include 3-cyclohexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, myrcene, farnesene, and chloroprene. In order to obtain a molded article having excellent mechanical strength and cold resistance, the conjugated diene preferably contains 1,3-butadiene or isoprene.

1.1.2. Monomers other than conjugated dienes (A) The component may contain repeating units derived from compounds other than conjugated dienes. As such a compound, an aromatic alkenyl compound is preferable. Among aromatic alkenyl compounds, an unsaturated monomer represented by the following general formula (1) is more preferable in order to produce a molded article having excellent mechanical strength, heat resistance, and cold resistance.

（一般式（１）中、Ｒ^１は単結合あるいは炭素数１〜３の２価の炭化水素基、Ｒ^３及びＲ^４はそれぞれ独立に炭素数１〜３のアルキル基、炭素数３〜１８のトリアルキルシリル基、又はいずれか一方が前記トリアルキルシリル基、他方が炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基若しくは炭素数１〜１００のオルガノシロキシ基、Ｒ^２は単結合、炭素数１〜２０のアルキレン基又はアルキリデン基、Ｒ^５は水素原子あるいはメチル基、ｎは０〜３の整数を示す。）

(In General Formula (1), R ¹ is a single bond or a divalent hydrocarbon group having 1 to 3 carbon atoms; R ³ and R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms; Trialkylsilyl group, or either one is the trialkylsilyl group, the other is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or 1 to 1 carbon atoms. 100 is an organosiloxy group, R ² is a single bond, an alkylene group or alkylidene group having 1 to 20 carbon atoms, R ⁵ is a hydrogen atom or a methyl group, and n is an integer of 0 to 3.

  Specific examples of the aromatic alkenyl compound include styrene, tert-butylstyrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, divinylbenzene, 1,1-diphenylstyrene, 1-vinylnaphthalene, 2-vinyl. Naphthalene, 2-vinylanthracene, 9-vinylanthracene, p-vinylbenzylpropyl ether, p-vinylbenzylbutyl ether, p-vinylbenzylhexyl ether, p-vinylbenzylpentyl ether, m-N, N-diethylaminoethylstyrene, p -N, N-diethylaminoethylstyrene, p-N, N-dimethylaminoethylstyrene, o-vinylbenzyldimethylamine, p-vinylbenzyldimethylamine, p-vinylbenzyldiethylamine, p-vinylbenzyldi ( -Propyl) amine, p-vinylbenzyldi (n-butyl) amine, vinylpyridine, 2-vinylbiphenyl, 4-vinylbiphenyl, p- [N, N-bis (trimethylsilyl) amino] styrene, p- [N, N-bis (trimethylsilyl) aminomethyl] styrene, p- {2- [N, N-bis (trimethylsilyl) amino] ethyl} styrene, m- [N, N-bis (trimethylsilyl) amino] styrene, p- (N -Methyl-N-trimethylsilylamino) styrene and p- (N-methyl-N-trimethylsilylaminomethyl) styrene. These monomers can be used alone or in combination of two or more. In order to produce a molded article excellent in mechanical strength, heat resistance, and cold resistance, it is preferable to include styrene or p-methylstyrene as a compound other than the conjugated diene.

  In the case where the component (A) has a repeating unit derived from a conjugated diene and a repetition derived from an aromatic alkenyl compound, the repeating unit derived from the conjugated diene of the component (A) and a repeating unit derived from an aromatic alkenyl compound; The mass ratio is preferably 100: 0 to 20:80 in order to keep the glass transition point of the component (A) moderately and to improve the mechanical strength and cold resistance of the molded body. More preferably, it is 40:60.

1.1.3. Composition of polymer block The component (A) is preferably a block copolymer in order to enhance compatibility with the component (C) and to more firmly bond the component (B) and the component (C). . Furthermore, a block polymer containing two or more polymer blocks selected from the following polymer blocks A to D is more preferable.

A block: A polymer block having a repeating unit amount derived from an aromatic alkenyl compound of 80% by mass or more.
B block: A polymer block having a repeating unit amount derived from a conjugated diene of 80% by mass or more and a vinyl bond content of less than 30 mol%.
C block: A polymer block having a repeating unit amount derived from a conjugated diene of 80% by mass or more and a vinyl bond content of 30 mol% or more and 90 mol% or less.
D block: a random copolymer block of a repeat derived from a conjugated diene and a repeat derived from an aromatic alkenyl compound, and a polymer block other than the above A to C.

  When the component (A) contains the C block, the molecular entanglement and compatibility with the olefin resin that is a kind of the component (C) are improved, so that the mechanical strength of the molded body is further improved. be able to. The vinyl bond content of the C block is more preferably 50 mol% or more and 90 mol% or less, and particularly preferably 60 mol% or more and 90 mol% or less. In order to remarkably improve the molecular entanglement and compatibility with the olefin resin, it is more preferable that the C block is hydrogenated.

  When the polymer block is a copolymer block formed of two or more compounds, the content of the repeating unit derived from a random type or an aromatic alkenyl compound or a repeating unit derived from a conjugated diene is the polymer block. A taper type that continuously changes may be used.

  The “vinyl bond content” in the present invention refers to a repeating unit derived from a conjugated diene that is incorporated in the polymer before hydrogenation in 1, 2 bond, 3, 4 bond, and 1, 4 bond bonding modes. Of these, the total proportion of units incorporated in 1, 2 bonds and 3, 4 bonds (based on mol%). The vinyl bond content (1,2 bond content and 3,4 bond content) can be calculated by an infrared absorption spectrum method (Morero method).

  Examples of the block polymer containing two or more polymer blocks selected from the polymer blocks A to D include, for example, AB, AC, AD, BC, BD. , [AB] x-Y, [AC] x-Y, [AD] x-Y, [BC] x-Y, [BD] x-Y, [BA ] X-Y, [C-A] x-Y, [D-A] x-Y, A-B-D, A-B-A, A-C-A, A-C-B, A-D -A, B-A-B, [A-B-D] x-Y, [A-B-A] x-Y, [A-C-A] x-Y, [A-C-B] x -Y, [A-D-A] x-Y, [B-A-B] x-Y, A-B-A-B, B-A-B-A, [A-B-A-B] x-Y, A-B-A-B-A, [A-B-A-B-A] x-Y, B-A-B-D, B-A-B-A, B-A-C -A, B-A-C-B, B A-D-A, [C-A-B-D] x-Y, [C-A-B-A] x-Y, [C-A-C-A] x-Y, [C-A- C—B] x—Y, [C—A—D—A] x—Y, C—A—B—A—B, C—B—A—B—A, C—A—B—A—C , [C-A-B-A-B] x-Y, C-A-B-A-B-A, and [C-A-B-A-B-A] x-Y (provided that x is an integer of 2 or more, and Y is a linking group). In the structure example, a structure surrounded by square brackets and having Y indicates that the block closest to Y is directly coupled to Y. For example, [A-C-B] x-Y indicates that x [A-C-B] are directly bonded to Y by the polymer block B. )

  When making the composition which concerns on this embodiment into a pellet shape, it is preferable to contain at least 1 sort (s) among A block and B block as a block component outside a conjugated diene block copolymer.

In order to improve the adhesion between the component (B) and the component (C) and to obtain a highly compatible composition of the component (A) and the component (C), among the above, A-C-A, A- It preferably has a structure of CB, [BC] xY, [AC] xY, [AD] xY, or ADA. A block polymer having a C block or a D block is preferable in that, when an olefin resin is used as the component (C), the compatibility with the resin is excellent, so that a good interface reinforcing effect can be obtained. Moreover, in order to improve adhesiveness with (B) component, it is preferable to have an amino group in A block.

  The linking group Y is a structural unit derived from a coupling agent. Examples of such a coupling agent include halogen compounds such as methyldichlorosilane, methyltrichlorosilane, butyltrichlorosilane, tetrachlorosilane, dibromoethane, tetrachlorotin, butyltrichlorotin, tetrachlorogermanium, and bis (trichlorosilyl) ethane. An epoxy compound such as epoxidized soybean oil; a carbonyl compound such as diethyl adipate, dimethyl adipate, dimethyl terephthalic acid and diethyl terephthalic acid; a polyvinyl compound such as divinylbenzene; and a polyisocyanate. A coupling agent can be used individually by 1 type or in combination of 2 or more types. In the coupling reaction, the reaction temperature is preferably 0 to 120 ° C, more preferably 50 to 100 ° C. The reaction time is preferably 1 to 30 minutes, more preferably 5 to 20 minutes.

1.1.4. Hydrogenation In order to improve the weather resistance and mechanical strength of the molded article according to this embodiment, the component (A) is preferably a hydrogenated polymer (hereinafter also referred to as “hydrogenation”). In particular, when an olefin resin is used as the component (C), by using a hydrogenated polymer as the component (A), the molecular entanglement and compatibility between the component (A) and the olefin resin are remarkable. To improve the adhesion between the component (C) and the component (B).

  The hydrogenation rate of the polymer (hereinafter also referred to as “hydrogenation rate”) can be controlled by changing the amount of the hydrogenation catalyst, the hydrogen pressure during the hydrogenation reaction, or the reaction time. For example, it is carried out in the presence of a hydrogenation catalyst at 20 to 150 ° C. under hydrogen pressure of 0.1 to 10 MPa. The hydrogenation rate is preferably 60% or more of double bonds such as vinyl bonds, more preferably 80% or more, and particularly preferably 95% or more. Hydrogenation may be performed after the polymerization reaction and then the modifier may be reacted, or the modifier may be reacted after the polymerization reaction and then hydrogenated.

  Examples of the hydrogenation catalyst and the specific hydrogenation method include, for example, JP-A-1-275605, JP-A-5-271326, JP-A-5-271325, JP-A-5-222115, and JP-A-11. -292924, JP-A 2000-37632, JP-A 59-133203, JP-A 63-5401, JP-A 62-218403, JP 7-90017, JP Examples thereof include hydrogenation catalysts and hydrogenation methods described in JP-A Nos. 43-19960 and 47-40473.

  The weight average molecular weight (Mw) of the hydrogenated polymer is preferably 30,000 to 2,000,000, more preferably 40,000 to 1,000,000, and particularly preferably 50,000 to 500,000. When the Mw is in the above range, the strength and dimensional stability of the molded product can be improved. Further, when the Mw is in the above range, the solution viscosity and the melt viscosity of the composition according to this embodiment become appropriate, and the moldability can be further improved. The “weight average molecular weight” is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

1.1.5. (A) Component Production Method The component (A) can be produced according to the method described in, for example, Japanese Patent No. 5402112, Japanese Patent No. 4840140, International Publication No. 2003/029299, and the like. Moreover, when (A) component is a block copolymer, it manufactures according to the method as described in patent 3134504 gazette, patent 3360411 gazette, patent 3988495 gazette, international publication 2014/014052, etc., for example. be able to. Specific examples of the method for producing the component (A) include the following methods (a) to (c). In addition, the polymer obtained by the following method can be hydrogenated by the above-mentioned method as needed.

1.1.5.1. Manufacturing method (a)
In the production method (a), a conjugated diene alone or a conjugated diene and an aromatic alkenyl compound are polymerized in the presence of at least one of an organic alkali metal compound and an organic alkaline earth metal compound. This is a method in which a denaturing agent is reacted with the coalescence. Hydrogenation may be performed as necessary. When the modifier is a compound having an alkoxysilyl group and an amino group, it can be introduced at a high introduction rate.

  The temperature at which the modifier is reacted is preferably 0 to 120 ° C. The reaction time is preferably 1 to 30 minutes. The amount of the modifier to be reacted with the polymer is preferably 10 mol% or more.

  Examples of the compound having an amino group include a halogenated amine, a compound represented by the following general formula (2), the following general formula (3), or the following general formula (4) having an alkoxysilyl group and an amino group. It is done.

  Examples of the halogenated amine include chloromethylamine, 2-bromoethylamine, 3-iodopropylamine, ethylchloromethylamine, bis (3-chloropropyl) amine, tris (4-bromobutyl) amine, N- (3- Aliphatic halogenated amines such as chloropropyl) morpholine; 2-chlorocyclohexylamine, bis (2-bromocyclohexyl) amine, N-methyl-2-chloropiperidine, 2-chlorocyclohexyldimethylamine, 2-chloropyrrolidine, 2 -Alicyclic halogenated amines such as bromopiperidine, 2-chloromorpholine, 4-chloropyrroline; 1-bromo-1-phenylmethylamine, 1-chloro-1-phenylethylamine, benzyl (3-bromopropyl) amine Benzyl-bis (chloromethyl Halogenated amines containing an aromatic ring such as amine, such as 2-chloromethylaniline, N-chloromethylaniline, N- (2-bromoethyl) aniline, N-methyl-N- (3-bromopropyl) aniline, 4 -Chloromethylpyrrole, 3-bromomethylindole, 2-chloromethylcarbazole, 2- (2-bromoethyl) imidazole, 3- (3-bromopropyl) pyrazole, 2-bromomethylnaphthyridine, 2-chloromethylquinazoline, 2- Aromatic halogenated amines such as iodomethylpyrimidine; 1-chloroethylenediamine, bis (2-amino-1-chloroethyl) amine, 2-bromohexamethylenediamine, tris (2-aminoethyl) amine, N, N, N 'N "N" -pentakis (chloromethyl) diethylenetriami Halogenated aliphatic polyamines and the like; 2-chloro-piperazine, 2-bromo-1,4,7-triazacyclononane cyclic halogenated polyvalent amine cyclo nonane, and the like.

<Compound represented by formula (2)>
R ⁶ _(4-mn) Si (OR ⁷ ) _m X _n (2)
In formula (2), R ⁶ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms. If R ⁶ is more, each of R ⁶ may be either different groups in the same group. R ⁷ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. If R ⁷ have multiple, each R ⁷ may be either different groups in the same group.

X is a group represented by the formula —A—X ′ (wherein A is an alkylene group having 1 to 20 carbon atoms, and X ′ is a group containing at least an N atom). When there are a plurality of X, each X may be the same group or different groups. Each X may be an independent substituent or may form a cyclic structure. m and n are integers of 1 to 3. The sum of m and n is an integer of 2-4.

  As the compound represented by the general formula (2), for example, compounds described in Japanese Patent No. 3988495, International Publication No. 2014/014052 and the like can be used. Among these, N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, N, N -Bis (trimethylsilyl) aminopropyldimethylmethoxysilane, N, N-bis (trimethylsilyl) aminopropyldimethylethoxysilane, N-methyl-N-trimethylsilylaminopropylmethyldiethoxysilane, 1- (3-triethoxysilylpropyl)- 2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane, 3-morpholinopropyldimethylmethoxysilane, 3- (4-methylpiperazin-1-yl) propyldimethylmethoxysilane, etc. Like .

<Compound represented by formula (3)>

In the general formula (3), R ^{8 to} R ¹¹ each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms, and R ¹² and R ¹³ represent an alkylene group having 1 to 20 carbon atoms. M is an integer of 1 or 2, and n is an integer of 1 to 3. In the compound represented by the general formula (3), the total number of alkoxy groups having 1 to 20 carbon atoms is preferably 4 or more.

  As the compound represented by the general formula (3), for example, compounds described in International Publication No. 2003/029299, International Publication No. 2014/014052 and the like can be used.

<Compound represented by formula (4)>

In the general formula (4), R ¹⁴ and R ¹⁵ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group, and R ¹⁹ represents an alkylene group having 1 to 20 carbon atoms. R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, or two of them are bonded to each other and together with the silicon atom to which they are bonded. To form a ring. m is an integer of 1 or 2.

Examples of the compound represented by the general formula (4) include 1-trimethylsilyl-2,2-diethoxy-1-aza-2-silacyclopentane and dimethoxysilyl compounds corresponding to these diethoxysilyl compounds, methyl Examples thereof include an ethoxysilyl compound, an ethylethoxysilyl compound, a methylmethoxysilyl compound, and an ethylmethoxysilyl compound.

  Examples of the organic alkali metal compound include an organic lithium compound and an organic sodium compound. Among these, an organolithium compound is preferable. Examples of the organic lithium compound include an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound.

  As the organic lithium compound, for example, compounds described in Japanese Patent No. 3988495 and International Publication No. 2014/014052 can be used. Among these, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, and 1,3-phenylene-bis- (3-methyl-1-phenylpentylidene) bislithium are preferable.

  The organic alkali metal compound may be an organic alkali metal compound having an amino group. Examples of such a compound include compounds represented by the following general formula (5) or the following general formula (6).

上記一般式（５）中、Ｒ^２０及びＲ^２１は双方が炭素数３〜１８のトリアルキルシリル基、又はいずれか一方が前記トリアルキルシリル基であって、他方が炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基若しくは炭素数１〜１００のオルガノシロキシ基を示す。Ｒ^２２は炭素数１〜２０のアルキレン基又はアルキリデン基を示す。

In the general formula (5), R ²⁰ and R ²¹ are both trialkylsilyl groups having 3 to 18 carbon atoms, or one of them is the trialkylsilyl group, and the other is alkyl having 1 to 20 carbon atoms. Group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms. R ²² represents an alkylene group having 1 to 20 carbon atoms or an alkylidene group.

上記一般式（６）中、Ｒ^２３は、炭素数１〜２０のアルキレン基又はアルキリデン基を示す。Ｒ^２４は炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基又は炭素数１〜１００のオルガノシロキシ基を示す。

In the general formula ^{(6), R 23} represents an alkylene group or an alkylidene group having 1 to 20 carbon atoms. R ²⁴ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms.

  As the organic alkali metal compound represented by the general formula (5) or (6), compounds described in Japanese Patent No. 3988495, International Publication No. 2014/014052 and the like can be used.

Examples of the organic alkaline earth metal compound include an organic magnesium compound, an organic calcium compound, an organic strontium compound, and an organic barium compound. Specific examples of the organic alkaline earth metal compound include, for example, ethylbutylmagnesium, di-n-butylmagnesium, di-n-hexylmagnesium, diethoxycalcium, calcium distearate, di-t-butoxystrontium, and diethoxybarium. , Diisopropoxy barium, diethyl mercapto barium, di-t-butoxy barium, diphenoxy barium, diethyl amino barium, barium distearate, diketyl barium and the like.

  Said organic alkali metal compound and organic alkaline earth metal compound can be used individually by 1 type or in combination of 2 or more types. Moreover, the usage-amount of an organic alkali metal compound or an organic alkaline-earth metal compound has preferable 0.02-15 mass with respect to 100 mass parts in total of monomers, such as a conjugated diene and another monomer.

1.1.5.2. Manufacturing method (b)
In the production method (b), at least one organic alkali metal compound and / or a polymer obtained by polymerizing a conjugated diene and an aromatic alkenyl compound, or a conjugated diene, an aromatic alkenyl compound, and another monomer are used. Alternatively, the modifier is reacted in the presence of an organic alkaline earth metal compound and at least one aliphatic amine compound. As the organic alkali metal compound, the organic alkaline earth metal compound, and the modifier, those exemplified in “1.1.5.1. Production method (a)” can be used.

  As the aliphatic amine compound, an aliphatic tertiary amine is preferable. Examples of the aliphatic tertiary amine include an ethylenediamine derivative, a propylenediamine derivative, or polyethyleneimine. Among these, ethylenediamine derivatives are preferable, and N, N, N ′, N′-tetramethylethylenediamine is more preferable.

  In the production method (b), a polymer containing a repeating unit derived from an aromatic alkenyl compound undergoes a modification reaction in a solvent. The isolated block copolymer may be dissolved in a solvent, or the copolymer solution after completion of the polymerization reaction or hydrogenation reaction may be used as it is.

  The organic alkali metal compound and the organic alkaline earth metal compound are preferably used in an amount of 0.01 to 5 times in molar ratio with respect to the aromatic alkenyl compound. In addition, the aliphatic amine compound is preferably 0.8 to 5 times in molar ratio with respect to the organic alkali metal compound or organic alkaline earth metal compound. The modifying agent is preferably 0.5 to 2 times the molar ratio of the organic alkali metal compound or organic alkaline earth metal compound.

  The first stage reaction is a step of mixing an aliphatic amine compound with at least one selected from the group consisting of an organic alkali metal compound and an organic alkaline earth metal compound into the copolymer solution. At least one selected from the group consisting of an organic alkali metal compound and an organic alkaline earth metal compound and the aliphatic amine compound may be added first, or may be added simultaneously. The reaction temperature is preferably 20 to 120 ° C. The reaction time is preferably 0 to 120 minutes. The second stage reaction is a process of mixing a denaturant with the first stage reaction solution. The reaction temperature is preferably 20 to 120 ° C. The reaction time is preferably 0 to 120 minutes. If necessary, hydrogenation may be performed after the second-stage reaction.

1.1.5.3. Manufacturing method (c)
In the production method (c), the conjugated diene alone or the conjugated diene and the aromatic alkenyl compound are polymerized in the presence of at least one of an organic alkali metal compound and an organic alkaline earth metal compound. In this method, the polymer is added to the polymer together with the peroxide and the modifier in a solution or in a kneader such as an extruder. As the organic alkali metal compound, the organic alkaline earth metal compound, and the modifier, those exemplified in “1.1.5.1. Production method (a)” can be used.

  The peroxide is not particularly limited, and 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1,3-bis (t-butyl And organic peroxides such as peroxyisopropyl) benzene. These peroxides can be used alone or in combination of two or more. It is preferable that the usage-amount of a peroxide is 0.001-3 mass parts with respect to 1 mass part of modifier | denaturants.

  The mixing and heating method is not particularly limited, and is an open type mixing roll, a non-open type Banbury mixer, a batch type melt kneader such as a kneader, a single screw extruder, a co-rotating continuous type Examples thereof include a continuous melt kneader such as a twin screw extruder and a different direction rotating type continuous twin screw extruder. The heating temperature is preferably 100 to 300 ° C. The heating time is preferably 10 to 900 seconds.

1.2. Fiber (B)
Generally, when a load such as a bending load is applied to the FRP molded body, the adhesion between the fiber and the matrix resin tends to be insufficient, and cracks are likely to occur from the interface between the fiber and the matrix resin. The cracks generated in this way propagate to the other interface between the fiber and the matrix resin, thereby causing further cracks and finally crossing the molded body to cause total destruction. However, even with a relatively long fiber such as component (B), the addition of component (A) as in the present invention improves the adhesion between component (B) and component (C), and bending It has become clear that mechanical properties such as strength and impact resistance can be effectively improved.

  The component (B) used in the present embodiment is a fiber having a fiber length of 3 mm or more and 50 mm or less. The lower limit value of the fiber length of the component (B) is preferably 4 mm or more, more preferably 5 mm or more. (B) The upper limit of the fiber length of a component becomes like this. Preferably it is 40 mm or less, More preferably, it is 30 mm or less. The FRP molded body obtained from the composition containing relatively long fibers as described above can improve both bending strength and impact strength in a balanced manner. A fiber having a fiber length of less than 3 mm tends to be insufficient in terms of improving the bending strength and impact strength of the obtained FRP molded product. On the other hand, a composition containing fibers having a fiber length exceeding 50 mm is not preferable because it is blocked by a hopper of a molding machine.

  The lower limit value of the fiber diameter of the component (B) is preferably 1 nm or more, more preferably 5 nm or more, and particularly preferably 10 nm or more. The upper limit of the fiber diameter is preferably 10 mm or less, more preferably 5 mm or less, still more preferably 3 mm or less, and particularly preferably 1 mm or less.

  The fiber length and fiber diameter of the component (B) can be measured by known methods. For example, the fiber length and the fiber diameter can be measured by observing the component (B) with a microscope. In addition, the fiber length and fiber diameter of the component (B) in the FRP molded product are observed with a microscope for filler residues collected by processing such as high-temperature ashing of the molded product, dissolution with a solvent, and decomposition with a reagent. Can be measured.

  The ratio (aspect ratio) between the fiber length and the fiber diameter of the component (B) is preferably 400 to 7500, more preferably 500 to 6000, and particularly preferably 700 to 4500. When the aspect ratio is within the above range, the mechanical properties of the molded body can be further improved. Moreover, when the aspect ratio is in the above range, deformation of the molded body and generation of anisotropy can be prevented, and a good appearance can be obtained.

  (B) A well-known material can be used as a component. The component (B) is, for example, alumina fiber, glass fiber, rock wool, potassium titanate fiber, zirconia fiber, ceramic fiber, silicon fiber, silicon nitride fiber, silica-alumina fiber, kaolin fiber, bauxite fiber, kayanoid fiber, boron. Inorganic fibers such as fiber, boron nitride fiber, magnesia fiber, potassium titanate whisper; polyester fiber, polyamide fiber, polyimide fiber, polyvinyl alcohol modified fiber, polyvinyl chloride fiber, polypropylene fiber, polybenzimidazole fiber, acrylic fiber , Carbon fiber, phenol fiber, nylon fiber, organic fiber such as cellulose (nano) fiber; Among these, carbon fiber is preferable.

  (B) You may modify the surface with a functional group as needed. Examples of such functional groups include (meth) acryloyl group, amide group, amino group, isocyanate group, imide group, urethane group, ether group, epoxy group, carboxy group, hydroxy group, and acid anhydride group. .

  The method for introducing the above functional group into the component (B) is not particularly limited. However, after the component (B) is introduced by directly reacting the sizing agent, or after the sizing agent is applied or impregnated to the component (B) Examples include a method of solidifying a sizing agent as necessary. Specifically, it can be produced based on the method described in JP2013-147663A.

  Types of sizing agents include, for example, acids, acid anhydrides, alcohols, halogenating reagents, isocyanates, alkoxysilanes, cyclic ethers such as oxirane (epoxy), epoxy resins, urethane resins, urethane-modified epoxy resins, epoxy-modified urethanes Resin, amine-modified aromatic epoxy resin, acrylic resin, polyester resin, phenol resin, polyamide resin, polycarbonate resin, polyimide resin, polyetherimide resin, bismaleimide resin, polysulfone resin, polyethersulfone resin, polyvinyl alcohol resin, polyvinyl The 1 type (s) or 2 or more types chosen from the group which consists of pyrrolidone resins are mentioned.

  There is no restriction | limiting in particular in the quantity of the sizing agent used when (B) component is made into a fiber bundle, For example, 0.1-10 mass parts is preferable with respect to 100 mass parts of (B) component.

  Hereinafter, carbon fibers suitable as the component (B) used in the present embodiment will be described.

  Examples of carbon fibers include PAN-based carbon fibers made from polyacrylonitrile fiber, pitch-based carbon fibers made from coal tar and petroleum pitch, cellulose-based carbon fibers made from viscose rayon, cellulose acetate, etc. Preferable examples include vapor-grown carbon fibers made from hydrogen or the like, and graphitized fibers thereof. In addition, the carbon fiber in this invention includes the form which processed the carbon nanotube and the graphene into the fiber form. These carbon fibers may be used alone or in combination of two or more.

1.3. Thermoplastic resin (C)
The composition according to this embodiment contains a thermoplastic resin (C). Examples of the component (C) include olefin resins; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polylactic acid; acrylic resins; styrene resins such as polystyrene, AS resin, and ABS resin; nylon 6, nylon 6, 6, nylon 12, semi-aromatic polyamide (nylon 6T, nylon 6I, nylon 9T), polyamides such as modified polyamide; polycarbonate, polyacetal, fluororesin, modified polyphenylene ether, polyphenylene sulfide, polyester elastomer, polyarylate, liquid crystal polymer (all Aromatic, semi-aromatic), polysulfone, polyethersulfone, polyetheretherketone, polyetherimide, polyamideimide, polyimide, and the like. Or it can be used in combination of two or more. Among these, an olefin resin is preferable.

  The molecular weight of the component (C) is preferably from 50,000 to 1,000,000, more preferably from 10,000 to 900,000, more preferably from 20,000 to 800,000 in terms of weight average molecular weight (Mw). It is particularly preferred. The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is not particularly limited, but is preferably 1 or more and 10 or less, and more preferably 2 or more and 7 or less.

  Hereinafter, the olefin resin suitably used in the present embodiment will be described.

  Examples of the olefin resin include homopolymers of α-olefins having about 2 to 8 carbon atoms such as ethylene, propylene, 1-butene; these α-olefins, ethylene, propylene, 1-butene, and 3-methyl. -1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene Binary or ternary (co) polymers with other α-olefins having about 2 to 18 carbon atoms such as 1-octadecene.

  Specific examples of the olefin resin include, for example, ethylene homopolymers such as branched low-density polyethylene and linear high-density polyethylene, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene- Ethylene-based polymers such as 1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-heptene copolymer, ethylene-1-octene copolymer Resin; propylene homopolymer, propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-4-methyl-1-pentene copolymer, propylene-ethylene-1-hexene copolymer 1-butene homopolymer, 1-butene-ethylene copolymer, 1-butene-propylene copolymer 1-butene resins coalescence and the like; 4-methyl-1-pentene homopolymer, 4-methyl-1-pentene - such as 4-methyl-1-pentene-based resins such as ethylene copolymers.

  These olefinic resins may be used alone or in combination of two or more. Among these, ethylene resins and propylene resins are preferable, propylene resins are more preferable, ethylene-propylene copolymers and propylene homopolymers are further preferable, and propylene homopolymers are particularly preferable. In particular, the component (A) is a block polymer having a conjugated diene polymer block having a repeating unit amount derived from a conjugated diene of 80% by mass or more and a vinyl bond content of 30% by mol to 90% by mol. In some cases, the propylene-based resin is preferable in that the compatibility with the component (A) is particularly good. In this case, the vinyl bond content of the polymer block is more preferably from 50 mol% to 90 mol%, particularly preferably from 60 mol% to 90 mol%. In addition, it is preferable that the component (A) is hydrogenated because compatibility with the propylene-based resin and molecular entanglement are significantly improved.

  The weight average molecular weight (Mw) of the olefin-based resin is preferably from 50,000 to 1,000,000, more preferably from 10,000 to 900,000 in order to improve the mechanical strength of the molded body. It is especially preferable that it is 20,000 or more and 800,000 or less. Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 1 or more and 10 or less, and more preferably 2 or more and 7 or less.

The olefin resin may be a combination of crystalline polyolefin and amorphous polyolefin. Examples of the amorphous polyolefin include homopolymers such as atactic polypropylene and atactic poly-1-butene, copolymers of propylene and other α-olefins, and 1-butene and other α-olefins. A copolymer etc. are mentioned.

1.4. Other components In addition to the above components, the composition according to the present embodiment includes, as other additives, an anti-aging agent, an antioxidant, a weathering agent, a metal deactivator, a light stabilizer, a heat stabilizer, and an ultraviolet absorber. Agent, antibacterial / antifungal agent, deodorant, conductivity enhancer, dispersant, softener, plasticizer, cross-linking agent, co-crosslinking agent, vulcanizing agent, vulcanizing aid, foaming agent, foaming aid, coloring An agent, a flame retardant, a vibration damping agent, a nucleating agent, a neutralizing agent, a lubricant, an anti-blocking agent, a dispersant, a fluidity improver, a release agent, and the like can be blended.

1.5. Content ratio of each component In the composition according to the present embodiment, the lower limit value of the content ratio of the component (A) is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the component (C) that is a matrix resin. More preferably, it is 0.5 mass part or more. (A) The upper limit of the content rate of a component becomes like this. Preferably it is 10 mass parts or less, More preferably, it is 5 mass parts or less. When the content ratio of the component (A) is in the above range, the component (A) can firmly bond the component (B) and the component (C). As a result, when a load such as a bending load is applied, the occurrence of cracks is suppressed from the interface between the component (B) and the component (C), and the bending strength of the molded body, the notched Charpy impact strength, the falling weight impact strength. It is thought that the mechanical strength such as is improved.

  Moreover, the lower limit of the content rate of (B) component is 10 mass parts or more with respect to 100 mass parts of (C) component which is matrix resin, Preferably it is 20 mass parts or more, More preferably, it is 25 mass parts That's it. (B) The upper limit of the content rate of a component is 100 mass parts or less with respect to 100 mass parts of (C) component which is a matrix resin, Preferably it is 50 mass parts or less, More preferably, it is 45 mass parts or less. (B) When the content rate of a component exists in the said range, the impact resistance of an obtained molded object, bending strength, and falling weight impact strength can be improved.

1.6. Method for Producing Composition The composition according to this embodiment can be produced by impregnating the component (B) with the component (A), the component (C), and other components as necessary. The impregnation method is not particularly limited, and after mixing the component (A) and the component (C), the mixture may be impregnated with the component (B). Further, the component (A) as a sizing agent may be applied to the component (B) and then impregnated with the component (C).

1.6.1. When using the component (A) as a sizing agent When using the component (A) as a sizing agent, the polymerization solution of the conjugated diene polymer obtained by the above-described method for producing the component (A) is used as it is as a sizing agent. May be used. Alternatively, after the component (A) is separated from the polymerization solution, the component (A) may be dissolved in a solvent and used as a solution, or dispersed in a dispersion medium and used as an emulsion (latex). By applying the component (A) as a sizing agent to the surface of the component (B) in advance, in the composition according to this embodiment, the component (A) is unevenly distributed at the interface between the component (B) and the component (C). be able to. As a result, even if the usage-amount of (A) component is small, the adhesiveness of (B) component and (C) component can be improved effectively. As a result, it is preferable because the mechanical strength of the molded body can be dramatically improved.

When the component (A) dissolved in a liquid medium is applied to the component (B) as a sizing agent, the liquid medium is not particularly limited. For example, aromatic hydrocarbons such as benzene, toluene and xylene; Alicyclic hydrocarbons such as pentane, cyclopentene and cyclohexane; aliphatic hydrocarbons such as pentane, hexane and heptane; alcohols such as methanol, ethanol, propanol, 2-propanol, ethylene glycol and glycerin; methylene chloride, chloroform and dichloride A hydrocarbon-based liquid medium such as a halogenated hydrocarbon such as ethylene can be used. Among these, aromatic hydrocarbons, alicyclic hydrocarbons, and aliphatic hydrocarbons are preferable, and aliphatic hydrocarbons are more preferable. The content ratio of the liquid medium in the composition according to the present embodiment is preferably 100 to 10000 parts by mass, more preferably 300 to 5000 parts by mass, and particularly preferably 600 to 3000 parts per 100 parts by mass of the component (A). Part by mass.

  When the component (A) dispersed in a liquid medium as an emulsion is applied to the component (B) as a sizing agent, the sizing agent can be prepared by a known emulsification method.

  When emulsifying, a surfactant may be added alone or in combination as necessary. Examples of such surfactants include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester; myristic acid, palmitic acid, Alkali metal salts and alkaline earth metal salts of fatty acids such as oleic acid, linolenic acid, stearic acid, lauric acid, araginic acid and ricinic acid; alkalis of resin acids such as rosin acid, disproportionated rosin acid and hydrogenated rosin acid Metal salts and alkaline earth metal salts; amine salts of hydroxyamines of long-chain fatty acid esters having a chain alkyl group or a cyclic alkyl group; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, higher alcohol sulfates, alkyls Anionic surfactants such as succinate; cationic surfactants such as alkyltrimethylammonium chloride, dialkylammonium chloride, benzylammonium chloride, tridecylbenzenehydroxyethylimidazole chloride; higher alcohols such as capryl alcohol and octyl alcohol Examples include phosphate esters, and monoesters of oleic acid and pentaerythritol, such as sorbitan monooleate. Copolymerizable surfactants such as sulfoesters of α, β-unsaturated carboxylic acids, sulfate esters of α, β-unsaturated carboxylic acids, and sulfoalkylaryl ethers can also be used. Water can be suitably used as the liquid medium.

  The use ratio of the surfactant is preferably 0.5 to 50 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the component (A). It is preferable that the amount of the surfactant used be in the above range because the emulsion tends to be more stable.

  The average particle size of the component (A) in the emulsion is preferably 0.02 to 100 μm, more preferably 0.1 to 10 μm, and particularly preferably 0.5 to 5 μm. When the average particle size of the component (A) in the emulsion is within the above range, the viscosity of the emulsion can be controlled to be easy to handle, and when the emulsion is stored, formation of a film at the gas-liquid interface can be suppressed. . The average particle diameter of the component (A) in the emulsion can be measured by using a particle size distribution measuring apparatus based on a laser diffraction / scattering method. An example of such a particle size distribution measuring apparatus is Microtrac MT3000 (manufactured by Nikkiso Co., Ltd.).

  In the emulsion, the use ratio of the dispersion medium is preferably 100 to 10,000 parts by mass, more preferably 300 to 5000 parts by mass, and particularly preferably 600 to 3000 parts by mass with respect to 100 parts by mass of the component (A).

In the fiber sizing agent, additives such as a pH adjuster, an antifoaming agent, a preservative, a crosslinking agent, a chelating agent, an oxygen scavenger, and a dispersing agent, which are usually blended in the latex field, can be blended. . Examples of the pH adjuster include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate; Gas; ammonia; organic amine compounds such as trimethylammonium and triethanolamine. Among these, alkali metal hydroxide, carbon dioxide, or ammonia is preferably used.

  When the component (A) is applied to the component (B) as a sizing agent and mixed with the component (C), the method for applying the component (A) to the component (B) is not particularly limited. Method, roller dipping method, roller transfer method, guide oiling method and the like can be used. The component (B) may be a single fiber or a fiber bundle, but a fiber bundle is preferable. (A) After apply | coating a component to (B) component, you may heat using a hot air, a hot plate, a roller, an infrared heater, etc.

1.6.2. Production conditions of the composition The composition according to the present embodiment is preferably produced by a pultrusion method in which fibers are impregnated with a matrix resin while drawing continuous fibers (roving). Specifically, a mixture obtained by adding the components (A), (C) and additives as necessary to a kneading extruder is supplied to the crosshead die in a molten state, and continuous fibers (roving) are passed through the crosshead die. While drawing, the mixture containing the matrix resin is impregnated into continuous fibers, cooled by a cooling device, and then cut to a desired length in a direction substantially perpendicular to the drawing direction. In addition, a continuous fiber can be made into the state of a fiber bundle (strand) by previously bundling a fiber using the above-mentioned (A) component or other sizing agents. The number of single yarns can be appropriately set according to the application from 1,000 (1K) to 60,000 (60K) single fiber bundles.

  In the pultrusion molding, the resin is impregnated while drawing a continuous reinforcing fiber bundle, and the matrix resin is supplied and impregnated from the kneading extruder or the like to the cross head while passing the fiber bundle into the cross head. Is the method. Other than this method, a method of impregnating a fiber bundle through an impregnation bath containing an emulsion, a suspension or a solution containing a matrix resin, spraying the matrix resin powder onto the fiber bundle or putting the powder therein Examples thereof include a method in which a fiber bundle is passed through a tank and resin powder is adhered to the fiber, and then the matrix resin is melted and impregnated. Further, the impregnation operation of the matrix resin in the pultrusion molding is generally performed in one stage, but it may be divided into two or more stages, and may be performed by different impregnation methods.

  The melt-impregnated product is extruded into a strand after the heating reaction, cooled to a temperature at which it can be cut, and cut into pellets by a pelletizer or the like. Therefore, the length of the pellet obtained in this way is substantially the same as the fiber length of the fiber (B). The shape of the pellet is not particularly limited, and specific examples include a columnar shape, a prismatic shape, a plate shape, and a die shape.

  For kneading the component (A) and the component (C), a conventionally known kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, or a roll, and a kneader formed by combining them can be used. In kneading, a method of kneading each component at once or a multistage divided kneading method in which a certain component is kneaded and then the remaining components are added and kneaded can be employed.

  In addition, when using an extruder as a kneading machine, 10-80 are preferable as L / D (ratio of the effective length (L) of the screw of an extruder, and the diameter (D) of a screw). As the kneading segment, a general-purpose kneading disk segment, a rotor segment, a VCMT (VARIOUS Clearance Mixing Technology) rotor segment, a twist kneading segment, a BMS (Backward Mixing single flight screw) segment, or the like can be used.

  The obtained mixture can be supplied to a single screw extruder or a twin screw extruder and melt kneaded again under the same kneading conditions as described above. For example, using the kneader, a step of melt-kneading the mixture of the component (A), the component (C) and other optional components under the kneading conditions described above is performed, and the steps are repeated a plurality of times as necessary. You may go.

  In addition, you may pre-mix a raw material component using a Henschel mixer etc. before melt-kneading. Further, before or after the melt-kneading, the raw material components or the kneaded mixture may be dried using a dehumidifying dryer, a hot air dryer, or the like, if necessary. At this time, the drying temperature is preferably 50 ° C. or more, and the drying time is preferably 2 hours or more.

2. Molded body The molded body according to the present embodiment is obtained by molding the above-described composition. In molding, it is preferable to select molding conditions that can suppress breakage of fibers contained in pellets. For this purpose, in a general molding method and molding apparatus, when the material is plasticized, the shear caused by the rotation of the screw is large, and the fiber may be broken. Therefore, it is preferable to use a molding machine having a plasticizing system developed for a long fiber reinforced thermoplastic resin of various molding machine manufacturers. Moreover, as a molding condition for maintaining the fiber length as much as possible, the temperature setting is 10 to 30 ° C. higher than the general plasticization temperature when molding in a state in which no reinforcing fiber is added to the matrix resin (non-reinforced). It is desirable to reduce shear due to plasticization. Furthermore, the design of the mold and / or die is not particularly limited, but the resin flow path is designed to be as wide as possible, and the shape of the resin flow path is also examined, and then the pressure is determined. It is desirable to apply a design with reduced loss in order to protect the fiber length.

  Thus, the fiber reinforced resin molded object disperse | distributed in the molded object shape | molded from a long fiber reinforced resin pellet can be achieved by taking the conditions which lengthen fiber length at the time of shaping | molding.

  As a molding method, a method similar to a method for molding a general thermoplastic composition can be applied. However, because of the above, conditions for reducing fiber shear due to plasticization can be appropriately selected. Methods such as molding, extrusion molding, hollow molding, foam molding, and press molding can be employed. Moreover, (B) component can be shape | molded in desired shapes, such as a sheet form, and the molded object can also be produced by impregnating the mixture of the (A) component and (C) component which were fuse | melted.

  The molded body according to the present embodiment makes use of its characteristics, for example, automobile materials such as automobile interior materials, outer plates, bumpers, etc., housings for household electrical products, home appliance parts, packaging materials, building materials, civil engineering materials, fisheries It is suitably used as a material and other industrial materials. Moreover, when carbon fiber is used as a fiber, it can also be used as an electromagnetic wave absorber by adjusting the degree of orientation of the carbon fiber in the resin.

3. EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. “Part” and “%” in Examples and Comparative Examples are based on mass unless otherwise specified. In addition, the measuring method of the physical property of the composition of this invention is as follows.

3.1. Physical property value of polymer (1) Vinyl bond content, etc. Vinyl bond content (1,2 bond content and 3,4 bond content) was determined by an infrared absorption spectrum method (Morero method). However, the unit of vinyl bond content is on a mol% basis. The total content of styrene units and p-methylstyrene units was determined by preparing a calibration curve by the infrared absorption spectrum method (Morello method). However, the unit of the content of styrene units is based on mass%.

(2) Hydrogenation rate The hydrogenation rate was calculated from a 400 MHz, ¹ H-NMR spectrum using carbon tetrachloride as a solvent.

(3) Weight average molecular weight (Mw)
The weight average molecular weight (Mw) is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) (HLC-8120, manufactured by Tosoh Corporation).
・ Developing solvent: THF
・ Measurement temperature: 40 ℃
-Column: TSKgel GMHxl

(4) Amino group content The amino group content is the content of amino groups (pieces) in one molecular chain of the polymer, and is represented by the following formula.
・ Amino group amount = (amino group (pieces) / polymer 1 molecular chain)
The amino group amount was calculated by the following method. First, Analy. Chem. The amino group concentration (mol / g) was determined by quantification by the amine titration method described in 564 (1952). That is, after purifying the obtained polymer, it was dissolved in an organic solvent, methyl violet was used as an indicator, and HClO ₄ / CH ₃ COOH was titrated until the color of the solution changed from purple to light blue. (Mol / g) was determined. Based on this amino group amount (mol / g), the amino group amount (mol / g) × molecular weight (g / mol) is calculated to calculate the content of amino groups (pieces) in one molecular chain of the polymer. Was calculated. In addition, the molecular weight was calculated | required from the number average molecular weight of polystyrene conversion calculated | required by GPC method.

3.2. Molding of composition, physical property measurement method and evaluation method (1) Bending strength ISO multi-purpose test piece (ISO3167) by injection molding using a long fiber screw in an injection molding machine “IS100GN” (model name) manufactured by Toshiba Machine Co., Ltd. A type A test piece defined in (1) was prepared. The test was performed according to ISO 179 at a fulcrum distance of 64 mm and a test speed of 2 mm / min. The test temperature is 23 ° C., and the unit is “MPa”. A case where the bending strength was 150 MPa or more was judged good and a case where the bending strength was less than 150 MPa was judged as poor.

(2) Charpy impact strength without notch An ISO multipurpose test piece was prepared by injection molding using a special screw for long fibers in an injection molding machine “IS100GN” (model name) manufactured by Toshiba Machine Co., Ltd. The test was subjected to evaluation according to ISO 178 without a notch. A hammer having a weight of 4 J was used for the striking arm. The test temperature is 23 ° C., and the unit is “kJ / m ² ”. The case where the Charpy impact strength without notch was 25 kJ / m ² or more was judged good, and the case where it was less than 25 kJ / m ² was judged as poor.

(3) Drop weight impact strength After molding a test piece having a size of 80 mm × 55 mm × 2.4 mm using a long fiber screw in an injection molding machine “J35AD” (model name) manufactured by Nippon Steel Works, Set on a high-speed impact tester “HITS-P10” (model name) manufactured by Shimadzu Corporation, drop weight test (punch tip diameter of weight: 12.7 mm, cradle hole diameter: 43 mm, test speed: 6.7 m / Second, test temperature: 23 ° C.), and the amount of puncture energy was measured according to JIS K7211-2. The unit is “J”. The case where the falling weight impact strength was 10 J or more was judged as good, and the case where it was less than 10 J was judged as bad.

(4) Interfacial shear strength One fiber with the prepared conjugated diene polymer (A) or commercially available sizing agent attached thereto is taken out and used with a composite material interface property evaluation apparatus (manufactured by Toei Sangyo Co., Ltd., model number “HM410”). Interfacial shear strength was evaluated by the microdroplet method. Specifically, the fiber to be measured is set in the apparatus, a molten drop of each type of thermoplastic resin (C) shown in Table 3 is formed on the fiber, cooled sufficiently at room temperature, and used for measurement. Samples were obtained. Thereafter, the measurement sample is set again in the apparatus, the drop is sandwiched between the apparatus blades, is run on the apparatus at a speed of 0.12 mm / min, and the maximum pulling load F when the fiber is pulled out from the drop is measured. The interfacial shear strength τ was calculated. The case where the interfacial shear strength was 20 MPa or more was judged good, and the case where it was less than 20 MPa was judged good.
τ = F / πDL
In the above formula,
F: Maximum stress (N) generated when the thermoplastic resin peels from the carbon fiber
D: Diameter of one carbon fiber (m)
L: Diameter of the thermoplastic resin in the axial direction of the fiber (m)
Respectively.

(5) Strand fluffing When pulling continuous fibers from the crosshead die, evaluation was performed according to the following criteria from the appearance of strand fluffing visually and the breaking state of component (B) due to fluffing.
-“3 points”: The component (B) does not come out of the strand, and the component (B) is not broken, so it is judged good.
“2 points”: The component (B) is partially removed from the strand, but the component (B) is not broken, so it is determined to be slightly defective.
-"1 point": Since the (B) component has slipped out of the strand as a whole and the (B) component has broken, it is determined to be defective.

(6) Blocking in the injection molding machine hopper When the pellets were put into the injection molding machine “J35AD” (model name) manufactured by Nippon Steel Works, the blocking state was confirmed in the hopper.
-“3 points”: No blocking in the hopper, and judged as good.
-“2 points”: blocking in the hopper, but blocking with a stick breaks, so it is judged to be slightly bad.
-“1 point”: blocking in the hopper, and even if attached with a stick, the blocking is not eliminated and it is judged as defective.

3.3. Production of hydrogenation catalyst A hydrogenation catalyst was produced by the following method.
A 1 L three-necked flask equipped with a stirrer and a dropping funnel was replaced with dry nitrogen, and 200 mL of anhydrous tetrahydrofuran and 0.2 mol of tetrahydrofurfuryl alcohol were added. Thereafter, n-butyllithium (hereinafter also referred to as “n-BuLi”) / cyclohexane solution (0.2 mol) was dropped into a three-necked flask at 15 ° C., and the reaction was carried out. A tetrahydrofuran solution was obtained.

  Next, a 1 L three-necked flask equipped with a stirrer and a dropping funnel was replaced with dry nitrogen, and 49.8 g (0.2 mol) of bis (η5-cyclopentadienyl) titanium dichloride and 250 mL of anhydrous tetrahydrofuran were added. added. Then, a tetrahydrofuran solution of tetrahydrofurfuryloxylithium obtained by the method described above was added dropwise over about 1 hour with stirring at room temperature. After about 2 hours, the reddish brown liquid was filtered and the insoluble part was washed with dichloromethane.

  Thereafter, the filtrate and the washing solution are combined and the solvent is removed under reduced pressure, whereby the hydrogenation catalyst [bis (η5-cyclopentadienyl) titanium (tetrahydrofurfuryloxy) chloride] (“[chlorobis (2,4 -Cyclopentadienyl) titanium (IV) tetrahydrofurfurylalkoxide] ”). The yield was 95%.

3.4. Synthesis of Conjugated Diene Polymer (A) [Synthesis Example 1]
Cyclohexane (25 kg), tetrahydrofuran (750 g), p-methylstyrene (750 g), and n-butyllithium (7.0 g) were added to a reaction vessel with an internal volume of 50 liters purged with nitrogen, and adiabatic polymerization from 50 ° C. Went. After completion of the reaction, the temperature was set to 20 ° C., 1,3-butadiene (3,750 g) was added, and adiabatic polymerization was performed. After 30 minutes, p-methylstyrene (500 g) was added for polymerization. Polymerization was stopped by reacting for 30 minutes while maintaining a hydrogen pressure of 1.0 MPa. Next, silicon tetrachloride (1.7 g) was added, and after 15 minutes, the hydrogenation catalyst (5.4 g) and diethylaluminum chloride (2.1 g) were added, and the hydrogen pressure was maintained at 1.0 MPa for 1 hour. Reacted. After the reaction, the reaction solution was returned to 70 ° C. and normal pressure and extracted from the reaction vessel to obtain a polymer solution. Water and the above polymer solution were added to the desolvation tank (ratio of 200 parts by mass of water with respect to 100 parts by mass of the polymer solution), and the temperature of the liquid phase of the desolvation tank was 95 ° C. and steam stripping for 2 hours ( The solvent was removed at a steam temperature of 190 ° C., and dried with a hot roll adjusted to 110 ° C. to obtain a hydrogenated conjugated diene block copolymer (1-B). A 7 L separable flask equipped with a stirrer was replaced with dry nitrogen, and the conjugated diene block copolymer (1-B) (500 g) was dissolved in cyclohexane (4,000 g). Next, N, N, N ′, N′-tetramethylethylenediamine (13.8 g) and s-butyllithium (7.6 g) were added and stirred for 15 minutes, and then N, N-bis (trimethylsilyl) aminopropyl was added. Methyldiethoxysilane (39.9 g) was added and allowed to react for 30 minutes. After distilling off the solvent with a rotary evaporator, it was vacuum dried at 60 ° C. for 18 hours to obtain a modified hydrogenated conjugated diene block copolymer (1-D).

[Synthesis Examples 2, 5-7]
Hydrogenated conjugated diene block copolymer (2-D), conjugated diene polymer (5-D), conjugated diene polymer using the components and amounts shown in Table 1 in the same manner as in Synthesis Example 1. (6-D) and a conjugated diene polymer (7-D) were obtained.

[Synthesis Example 3]
Cyclohexane (25 kg), tetrahydrofuran (750 g), styrene (750 g), and n-butyllithium (7.0 g) were added to a reaction vessel having an internal volume of 50 liters purged with nitrogen, and adiabatic polymerization was performed from 50 ° C. . After completion of the reaction, the temperature was set to 20 ° C., 1,3-butadiene (3,750 g) was added, and adiabatic polymerization was performed. After 30 minutes, styrene (500 g) was added, polymerization was further performed, and reaction was performed for 30 minutes. Then, the conjugated diene polymer (3-A) which is a conjugated diene block copolymer was obtained by performing a solvent removal and drying by the method similar to the synthesis example 1.

[Synthesis Example 4]
Cyclohexane (25 kg), tetrahydrofuran (750 g), styrene (750 g), and n-butyllithium (7.0 g) were added to a reaction vessel having an internal volume of 50 liters purged with nitrogen, and adiabatic polymerization was performed from 50 ° C. . After completion of the reaction, the temperature was set to 20 ° C., 1,3-butadiene (3,750 g) was added, and adiabatic polymerization was performed. After 30 minutes, styrene (500 g) was added for polymerization. Polymerization was stopped by reacting for 30 minutes while maintaining a hydrogen pressure of 1.0 MPa. Next, silicon tetrachloride (1.7 g) was added, and after 15 minutes, the hydrogenation catalyst (5.4 g) and diethylaluminum chloride (2.1 g) were added, and the hydrogen pressure was maintained at 1.0 MPa for 1 hour. Reacted. After the reaction, the reaction solution was returned to 70 ° C. and normal pressure and extracted from the reaction vessel to obtain a polymer solution. Thereafter, solvent removal and drying were carried out in the same manner as in Synthesis Example 1 to obtain a conjugated diene polymer (4-B) which is a hydrogenated conjugated diene block copolymer.

  Table 1 shows the reagents and analysis results used for the reaction of each copolymer obtained.

3.5. Fabrication of molded body (1)
In Examples 1-7 and Comparative Examples 1-3, pellets produced by the following method were evaluated.

  Carbon fiber B-1 (manufactured by Toray Industries, Inc., trade name “T700SC-12K-50C”) is produced with the composition shown in Table 2 while pulling the carbon fiber roving shown in Table 2 through a crosshead whose path is processed into a wave shape. The mixture of component (A) and component (C) was supplied from an extruder connected to a crosshead, impregnated with carbon fibers in a molten state (260 ° C.), taken as a strand through a shaping die, and cut As a result, pellets having the compositions shown in Table 2 were obtained.

3.6. Fabrication of molded body (2)
In Examples 8 to 11 and Comparative Examples 4 to 7, pellets produced by the following method were evaluated.

  100 g of the conjugated diene polymer (A) shown in Table 3 and 900 g of cyclohexane shown in Table 3 were put into an Erlenmeyer flask and dissolved at room temperature to prepare a solution of the conjugated diene polymer (A). Thereafter, 350 g of water in a 2 L glass beaker, 640 g of the above solution, 25.6 g of 25% aqueous solution of Emulgen 147 (trade name, polyoxyethylene lauryl ether) manufactured by Kao Corporation, Neogen S-20F manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 3.2 g of a 10% aqueous solution of sodium dodecyl benzene sulfonate) was sequentially added, and the mixture was stirred at 13,000 rpm for 10 minutes using a homomixer MARK II (trade name) manufactured by Tokushu Kika Kogyo Co., Ltd. Thereafter, the emulsion was transferred to a rotary evaporator N-11 (trade name) manufactured by Tokyo Rika Kikai Co., Ltd., and the water-based emulsion dispersion was prepared such that cyclohexane was dissolved and the concentration of the conjugated diene polymer (A) was adjusted to 7%. (Sizing agent) was obtained.

  Carbon fiber B-0 (trade name “Torayca T700SC-12000-50C” manufactured by Toray Industries, Ltd., where the sizing agent was removed with acetone) was continuously immersed in a treatment bath filled with the adjusted aqueous emulsion dispersion (sizing agent). Then, a predetermined amount of the conjugated diene polymer (A) was adhered to the fiber (B). Subsequently, it was dried by continuously passing through an oven at 120 ° C. for 5 minutes. The interface shear strength measurement mentioned above was performed about the fiber (B) to which the obtained conjugated diene polymer (A) was adhered.

  Further, the component (C) shown in Table 3 is connected to the crosshead while the fiber (B) to which the conjugated diene polymer (A) thus prepared is attached is pulled through the crosshead processed into a wave shape. After being impregnated into the fiber (B) to which the conjugated diene polymer (A) was adhered in a molten state (260 ° C.), the strand was taken out as a strand through a shaping die and cut, A pellet having the composition shown in FIG.

3.7. Evaluation results Tables 2 to 3 show compositions and evaluation results of the compositions of the examples and comparative examples.

In Tables 2 to 3, abbreviations of the component (B) and the component (C) are as follows. [Fiber (B)]
-Fiber (B-1): manufactured by Toray Industries, Inc., trade name “T700SC-12K-50C”
[Thermoplastic resin (C)]
・ PP: Polypropylene made by Nippon Polypro Co., Ltd. “NOVATEC MA1B” (trade name)

  According to Examples 1-7, it turned out that it is improving significantly at the point of bending strength, notch Charpy strength, and falling weight impact strength compared with the comparative example 1 which does not contain (A) component. In Examples 1 to 7, when the continuous fiber was taken from the crosshead die, the component (B) did not come out of the strand, and the component (B) was not broken.

  According to Comparative Example 1, since it did not contain the component (A), it was found that it was inferior in bending strength, unnotched Charpy strength, and falling weight impact strength as compared with the Example.

  According to Comparative Examples 2 and 3, since the component (A) does not have an amino group, the component (B) and the component (C) cannot be firmly bonded to each other in the obtained molded body. It was found that bending strength, unnotched Charpy strength, and falling weight impact strength are hardly improved even when compared with Comparative Example 1 that does not include the.

  According to Examples 8-11, compared with the comparative example 4 which does not contain (A) component, it has improved significantly in terms of interfacial shear strength, bending strength, bending strength, unnotched Charpy strength, and falling weight impact strength. I found out. In Examples 8 to 11, when the continuous fibers were taken from the crosshead die, the component (B) did not come out of the strand, and the component (B) was not broken. Further, in Examples 8 to 11, there was no blocking in the injection molding machine hopper.

  According to Comparative Example 4, since the component (A) was not included, it was found that the interfacial shear strength, bending strength, bending strength, unnotched Charpy strength, and falling weight impact strength were inferior to those of the Example. .

  According to Comparative Examples 5, 6, and 7, since the component (A) does not have an amino group, the component (B) and the component (C) cannot be firmly bonded in the obtained molded body. It was found that the bending strength and drop weight impact strength were hardly improved even when compared with Comparative Example 4 containing no component A).

  According to Comparative Example 7, since the fiber length of the component (B) was 60 mm, when the pellet was put into the injection molding machine, it was blocked in the hopper, and the blocking was not eliminated even if it was attached with a stick.

The present invention is not limited to the above embodiment, and various modifications can be made. The present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same functions, methods, and results, or configurations that have the same objects and effects). The present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration. Furthermore, the present invention includes a configuration that achieves the same effect as the configuration described in the above embodiment or a configuration that can achieve the same object. Furthermore, the present invention includes a configuration obtained by adding a known technique to the configuration described in the above embodiment.

Claims (5)

Containing a conjugated diene polymer (A), a fiber (B), and a thermoplastic resin (C);
Containing 10 to 100 parts by mass of the fiber (B) with respect to 100 parts by mass of the thermoplastic resin (C);
The conjugated diene polymer (A) has an amino group,
The composition whose fiber length of the said fiber (B) is 3 mm or more and 50 mm or less.   The composition of Claim 1 whose content rate of the said conjugated diene polymer (A) is 0.1 mass part or more and 10 mass parts or less with respect to 100 mass parts of said thermoplastic resins (C).   The composition according to claim 1 or 2, wherein the fiber (B) is a carbon fiber.   The composition according to any one of claims 1 to 3, wherein the thermoplastic resin (C) is an olefin resin. The molded object obtained by shape | molding the composition as described in any one of Claims 1 thru | or 4.