JP2017048313A - Composition and molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition capable of obtaining a molded body excellent in mechanical strength such as impact resistance and bending strength even when a reproduced fiber collected by recycling or a fiber having a short fiber length is used.SOLUTION: A composition contains a polymer (A) having an amino group, a fiber (B), and a thermoplastic resin (C). The fiber (B) is a recycled fiber. The composition contains a polymer (A) having an amino group, a fiber (B), and a thermoplastic resin (C). An average fiber length of the fiber (B) is 20 μm-500 μm.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.

  Among the raw materials that can be recovered from FRP, cracked resin can be used for fuel and petroleum products. However, fibers such as glass fiber and carbon fiber are strong materials, and realistic treatment methods other than landfill are now available. There is no place. Therefore, technologies for recycling these fibers are being studied from the viewpoint of resource recycling.

  For example, as a technique for collecting and recycling carbon fiber (CF) from CFRP, a method of collecting and recycling carbon fiber from CFRP using a treatment liquid containing potassium phosphate or hydrated phosphate (for example, patents) Reference 1), a method of recovering carbon fiber from CFRP using a depolymerization catalyst selected from alkali metal compounds and salts thereof (for example, see Patent Document 2), and thermal decomposition of resin components from CFRP A method of removing the carbon fiber and removing the carbon fiber (for example, see Patent Document 3) has been proposed.

JP 2003-55475 A JP 2008-7630 A JP 2008-285601 A

  However, the recycled fiber collected by recycling has a fiber length shorter than that of the initial fiber due to the pulverization processing of the FRP molded product. Moreover, the sizing agent adhering to the fiber is peeled off or decomposed by using a solvent in the recovery step or by heat treatment. Therefore, when the recycled fiber collected by recycling is reused as FRP, there is a problem that mechanical properties such as impact resistance and bending strength of FRP are remarkably deteriorated.

  Accordingly, some aspects of the present invention solve at least a part of the above problems, and even when using recycled fibers collected by recycling or fibers having a short average fiber length, impact resistance And a composition from which a molded article excellent in mechanical strength such as bending strength can be 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:
A polymer (A) having an amino group;
Fiber (B),
A thermoplastic resin (C);
And the fiber (B) is a recycled fiber.

[Application Example 2]
One aspect of the composition according to the present invention is:
A polymer (A) having an amino group;
Fiber (B),
A thermoplastic resin (C);
The average fiber length of the said fiber (B) is 20 micrometers-500 micrometers, It is characterized by the above-mentioned.

[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, even if the added fiber is a recycled fiber or a short fiber having an average fiber length of 20 μm to 500 μm, the molding is excellent in mechanical strength such as impact resistance and bending strength. The body can be made.

  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 polymer (A) having an amino group is “(A) component”, the fiber (B) is “(B) component”, and the thermoplastic resin (C) is “(C) component”. Sometimes abbreviated.

1. Composition In general, when a load such as a bending load is applied to the FRP molded body, cracks are generated from the interface between the fiber and the matrix resin. The cracks generated in this manner propagate to the interface between the other fibers and the matrix resin, thereby further inducing cracks and finally crossing the molded body to cause total destruction. In particular, the occurrence of cracks when a load is applied to the FRP compact is easily induced by stress concentration at the fiber end. Moreover, since the fiber edge part per weight increases relatively, so that a fiber becomes short, the crack of a FRP molded object tends to generate | occur | produce easily. As a result, the mechanical strength of the molded body using short fibers tends to decrease.

  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 realize this, the composition according to the present embodiment further contains a polymer (A) having an amino group in addition to the fibers (B) as the reinforcing fibers and the thermoplastic resin (C) as the matrix resin. The configuration of “Yes” is adopted. Hereinafter, each component contained in the composition according to the present embodiment will be described.

1.1. Polymer having amino group (A)
The composition according to this embodiment includes a polymer (A) having an amino group. The component (A) is considered to improve the dispersibility of the component (B) in the composition. Furthermore, in the molded body according to the present embodiment, the (B) component and the (C) component when a load such as a bending load is applied by firmly bonding the (B) component and the (C) component. It is thought that the occurrence of cracks from the interface is suppressed, and the mechanical strength such as the bending strength, unnotched Charpy impact strength and falling weight impact strength of the molded body is improved.

The component (A) used in this embodiment has an amino group as a functional group. The method for imparting an amino group to a polymer is not particularly limited, such as a method for imparting an amino group to a polymer with a modifier having an amino group, a method for obtaining a component (A) by polymerizing a monomer having an amino group, etc. Is exemplified. Moreover, it is good also as a structure into which the amino group was introduce | transduced by making the compound which has an amino group react with a polymer. The component (A) may have an amino group as a functional group, but may have an alkoxysilyl 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, the adhesion to the component (B) is further strengthened, and the mechanical strength of the molded product obtained by molding the composition according to this embodiment is considered to be 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) preferably has a repeating unit derived from a conjugated diene. The component (A) may have a repeating unit derived from a monomer other than the conjugated diene 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 polymer. 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 having a repeating unit derived from a conjugated diene will be described in detail.

1.1.1. The conjugated diene (A) component preferably has a 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. The monomer (A) other than the conjugated diene may have a repeating unit derived from a compound other than the conjugated diene. 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, which 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 significantly improve the molecular entanglement and compatibility with the olefin resin, the C block is more preferably 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. [A-B] x-Y, [A-C] x-Y, [A-D] x-Y, [BC] x-Y, [BD] x-Y, [B
-A] 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-- -B-A-B-A, it includes [C-A-B-A-B-A] x-Y (where, x is an integer of 2 or more, 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 that an amino group is introduce | transduced into 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 polymer, 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. Can do. 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.

  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 halogenated amines, compounds 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. Can be mentioned.

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-methyl -N-trimethylsilylaminopropylmethyldiethoxysilane, 1- (3-triethoxysilylpropyl) -2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane, 3-morpholinopropyl Dimethylmethoxysilane, 3- (4-methylpiperazin-1-yl) propyldimethylmethoxysilane and the like are preferable.

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

  The first stage reaction is a step of mixing an organic alkali metal compound and / or an organic alkaline earth metal compound and an aliphatic amine compound into the copolymer solution. Either the organic alkali metal compound and / or the 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), 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. 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)
A recycled fiber can be used as the fiber (B). The recycled fiber refers to a fiber that can be reused among the collected fibers after removing the matrix resin from the fiber reinforced resin (FRP) that has become waste material.

  Generally, methods for decomposing a resin used when recovering fibers from FRP include methods such as thermal decomposition, chemical decomposition, and photodecomposition. However, regardless of which method is used, since the FRP is pulverized by the pulverizer at the pretreatment stage, the average fiber length of the recovered fibers becomes shorter than the unused fibers. Therefore, when recycled fibers collected by recycling are reused as FRP, mechanical properties such as impact resistance and bending strength of FRP are significantly deteriorated as compared with the case of adding unused fibers.

  However, even if the added fiber (B) is a fiber having a short average fiber length such as a recycled fiber, by adding the component (A) as in the present invention, a machine such as impact resistance and bending strength can be obtained. It became clear that the physical characteristics could be improved.

  The lower limit value of the average fiber length of the component (B) is preferably 20 μm or more, more preferably 50 μm or more, and particularly preferably 80 μm or more. The upper limit of the average fiber length is preferably 500 μm or less, more preferably 470 μm or less, and particularly preferably 450 μm or less. When the component (B) is a recycled fiber recovered from the FRP, the average fiber length of the fiber is likely to be within the above range because it undergoes a pulverization treatment step by a pulverizer. When the average fiber length of component (B) is within the above range, mechanical properties such as impact resistance and bending strength are significantly deteriorated even when component (B) is added to FRP. By adding, mechanical properties such as impact resistance and bending strength are improved.

  Moreover, the lower limit value of the average 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 average fiber diameter is preferably 200 μm or less, more preferably 150 μm, still more preferably 100 μm or less, and particularly preferably 70 μm or less.

  (B) The average fiber length and average fiber diameter of a component can be measured by a well-known method. For example, the component (B) can be observed with a microscope, the fiber length and the fiber diameter can be measured for 300 randomly selected fibers, and the average values can be calculated as the average fiber length and the average fiber diameter, respectively. In addition, the average fiber diameter and average fiber length of the fibers in the molded product were determined by randomly observing the filler residue collected by processing such as high-temperature ashing of the molded product, dissolution with a solvent, and decomposition with a reagent under a microscope. The fiber length and the fiber diameter of each of the 300 selected fibers can be measured, and the average values can be calculated as the average fiber length and the average fiber diameter, respectively.

  The ratio (aspect ratio) between the average fiber length and the average fiber diameter of the component (B) is preferably 2 to 80, more preferably 5 to 75, and particularly preferably 10 to 70. When the aspect ratio is in the above range, the mechanical properties of the molded product can be 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. Further, the component (B) may be in a fiber bundle (strand) state. The fiber bundle can be produced by bundling short fibers using a sizing agent. The number of single yarns can be appropriately set according to the application from 1,000 (1K) to 60,000 (60K) single fiber bundles.

  As the component (B), 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, cananoid fiber, Inorganic fibers such as boron 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 Examples thereof include organic fibers such as fibers, carbon fibers, phenol fibers, nylon fibers, and cellulose (nano) fibers. Among these, cellulose fiber, carbon fiber, and glass fiber are preferable, and carbon fiber is particularly preferable.

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

  The method for introducing the above functional group into the component (B) is not particularly limited, but a method in which the component (B) is introduced by directly reacting with the sizing agent, or after applying or impregnating the component (B) with the sizing agent 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 One type or two or more types selected from the group consisting of pyrrolidone resins may be 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 short fibers and recycled fibers 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 may 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-based resin such as propylene homopolymer, propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer; 1-butene homopolymer, 1-butene-ethylene copolymer, 1-butene- 1-butene resin such as propylene copolymer; 4-methyl-1-pentene homopolymer, 4-methyl-1-pentene-ethylene copolymer A resin such as 4-methyl-1-pentene resin polymer, and the like.

  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 more 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 0.05 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 0.1 mass part or more, Most 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 30 mass parts or less, More preferably, it is 20 mass parts or less, More preferably, it is 10 mass parts or less, Most 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 ratio of the component (B) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, particularly preferably 10 parts by mass with respect to 100 parts by mass of the component (C) which is a matrix resin. That's it. (B) The upper limit of the content rate of a component becomes like this. Preferably it is 150 mass parts or less, More preferably, it is 100 mass parts or less, More preferably, it is 70 mass parts or less, Most preferably, it is 50 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. Manufacturing method of composition The composition which concerns on this embodiment can be manufactured by mixing (A) component, (B) component, (C) component, and another component as needed. The mixing method is not particularly limited as long as the component (B) is uniformly dispersed in the composition. The composition which concerns on this embodiment may mix and knead | mix the (A) component, (B) component, and (C) component collectively, and obtains the composition of (A) component and (C) component. This may be used as a master batch and mixed with the component (B) to form a composition.

1.6.1. Manufacturing condition of composition The composition according to the present embodiment is a method for manufacturing a short fiber reinforced resin by kneading the component (A), the component (B), the component (C), and other components as necessary. It can be manufactured according to. The kneading temperature is preferably 150 to 350 ° C., and the shear rate is preferably 100 to 20000 s ⁻¹ . The specific energy obtained by dividing the electric power consumption of the kneader per unit time by the kneading amount per unit time is preferably 0.1 to 10 kWh / kg.

  For kneading, 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 the production of the composition according to this embodiment, among the above kneaders, a twin-screw extruder is particularly preferable, and any of the same-direction rotation type and the different-direction rotation type can be suitably used. For example, what connected the twin-screw extruder and the twin-screw extruder, what connected the twin-screw extruder and the single-screw extruder, and what connected the continuous kneader and the twin-screw extruder are mentioned.

  In addition, when using an extruder as a kneading machine, L / D (ratio of the effective length (L) of the screw of an extruder, and the diameter (D) of a screw) has preferable 30-80. 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 a mixture of the component (A), the component (B), the component (C) and other optional components under the kneading conditions described above is performed, and the step is performed as necessary. May be repeated a plurality of times.

  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. As a molding method, the same method as a general thermoplastic composition molding method can be applied. Specifically, methods such as injection 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.

  By producing a molded body using the composition according to the present embodiment, a molded body having good mechanical strength can be produced.

  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. Physical property measurement method and evaluation method of composition (1) Bending strength ISO multi-purpose test piece (Type A test defined by ISO 3167) by injection molding using an injection molding machine “IS100GN” (model name) manufactured by Toshiba Machine Co., Ltd. Piece). 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 130 MPa or more was judged good and a case where the bending strength was less than 130 MPa was judged as poor.

(2) Notch-free Charpy impact strength An ISO multipurpose test piece was prepared by injection molding using 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 an injection molding machine “J35AD” (model name) manufactured by Nippon Steel Works, a high speed manufactured by Shimadzu Corporation Set on impact tester “HITS-P10” (model name), drop weight test (punch tip diameter of weight: 12.7 mm, cradle hole diameter: 43 mm, test speed: 6.7 m / sec, test temperature: 23 ° C) and JIS
The amount of puncture energy was measured according to K7211-2. The unit is “J”. The case where the falling weight impact strength was 3 J or more was judged good, and the case where it was less than 3 J was judged good.

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 polymer (A) having amino group [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 is removed at a steam temperature of 190 ° C. and dried with a hot roll adjusted to 110 ° C. to obtain a conjugated diene polymer (1-B) which is a hydrogenated modified conjugated diene block copolymer. It was. Next, a 7-L separable flask equipped with a stirrer was replaced with dry nitrogen, and the conjugated diene 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 conjugated diene polymer (1-D) which is a modified hydrogenated conjugated diene block copolymer.

[Synthesis Examples 2, 5-7]
In the same manner as in Synthesis Example 1, using the components and amounts shown in Table 1, conjugated diene polymer (2-D), conjugated diene polymer (5-D), conjugated diene polymer (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. Production of fiber (B) [fiber (Ba): grinding method]
The CFRP molded product produced in Comparative Example 4 to be described later is coarsely pulverized with a solid pulverizer, passed through a screen diameter of 12 mm, and then passed through a pulverizer again to pass a screen diameter of 1 mm, whereby a recycled fiber in a state where PP resin is adhered. A pulverized product containing (fiber (Ba)) was obtained. This pulverized product was used as fiber (B) as it was. When the obtained pulverized product was put in a crucible and baked at 400 ° C. for 1 hour, the carbon fiber content was 16 mass%, the average fiber diameter was 7 μm, and the average fiber length was 120 μm.

[Fiber (Bb): Thermal decomposition method]
A CFRP golf shaft using an epoxy resin as a matrix is coarsely pulverized by a solid pulverizer, passed through a screen diameter of 12 mm, and then again passed through a pulverizer to pass a screen diameter of 1 mm, so that the carbon fiber in a state where the epoxy resin is attached. To obtain a pulverized product. Next, this pulverized product is filled in a crucible at a filling rate of 80% by volume, and is thermally decomposed in an electric furnace at 400 ° C. for 1 hour under the condition that the pulverized product is filled with a decomposition gas, with an average fiber diameter of 7 μm and an average fiber length of 500 μm. Recycled fiber (fiber (B-b)) was obtained.

[Fiber (Bc), Fiber (Bd), Fiber (Be)]
In the same manner as the fiber (B-b), classification was performed with a sieve having different mesh sizes of 200 to 800 μm to obtain each classified product of carbon fibers having a uniform fiber length and attached with an epoxy resin. Next, each classified crushed product is filled in a crucible at a filling rate of 80% by volume, and is thermally decomposed in an electric furnace at 400 ° C. for 1 hour under the condition that the pulverized material is decomposed, and the average fiber diameter is 7 μm. Recycled fibers having fiber lengths of 300 μm (fiber (Bc)), 80 μm (fiber (Bd)), and 200 μm (fiber (Be)) were obtained.

3.6. Examples 1 and 8 and Comparative Example 1
With respect to the components (A), (B), and (C) shown in Table 2 or Table 3, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-], which is an antioxidant, is used. Hydroxyphenyl) propionate] (trade name “ADK STAB AO-60”, manufactured by ADEKA) 0.1 parts by mass and tris (2,4-di-tert-butylphenyl) phosphite (trade names “ADK STAB 2112”, ADEKA) 0.1 parts by mass) and dry blended at room temperature. Subsequently, this mixture was injection-molded using an injection molding machine “IS100GN” (model name) manufactured by Toshiba Machine Co., Ltd., to produce an ISO multipurpose test piece, which was used for evaluation.

3.7. Examples 2-7, 9, 10, Comparative Examples 2-5
Antioxidant pentaerythritol tetrakis [3- (3,5-di-tert] is used with respect to the types and parts by mass of (A) component, (B) component, and (C) component shown in Table 2 or Table 3. -Butyl-4-hydroxyphenyl) propionate] (trade name “ADK STAB AO-60”, manufactured by ADEKA) 0.1 parts by mass and tris (2,4-di-tert-butylphenyl) phosphite (trade name “ Adeka Stub 2112 "(manufactured by ADEKA) (0.1 part by mass) was added and hand blended at room temperature. Next, this mixture was supplied to a single screw extruder “FS40” (model name) manufactured by Ikekai Co., Ltd., and melt kneaded to obtain pellets. In addition, the cylinder setting temperature at the time of melt-kneading was 140 to 220 degreeC. That is, the temperature gradient was set so that the temperature near the base of the hopper was 140 ° C. and the temperature near the outlet was 220 ° C. Then, after sufficiently drying the pellets, injection was performed using an injection molding machine “IS100GN” (model name) manufactured by Toshiba Machine Co., Ltd. with a temperature gradient of 170 ° C. to 220 ° C. similarly to the above. By molding, an ISO multipurpose test piece was prepared and used for evaluation.

3.8. Comparative Example 6
Antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-) with respect to the types and parts by mass of (A) component, (B) component, and (C) component shown in Table 3 4-hydroxyphenyl) propionate] (trade name “ADK STAB AO-60”, manufactured by ADEKA) and 0.1 part by mass of tris (2,4-di-tert-butylphenyl) phosphite (trade name “ADK STAB 2112”) 0.1 parts by mass of ADEKA) and 1 part by mass of acid-modified polypropylene (trade name “Yumex 1001”, Sanyo Chemical Industries) were added and dry blended at room temperature. Next, this mixture was injection-molded using an injection molding machine “IS100GN” (model name) manufactured by Toshiba Machine Co., Ltd., so that an ISO multipurpose test piece was prepared for evaluation.

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

In Table 2 and Table 3, the abbreviations of the component (B) and the component (C) are as follows.
[Fiber (B)]
Fibers (Ba) to (Be): Carbon fibers recycled by the above method. Fiber (Bf) virgin: Trade name “HT C702”, carbon fiber manufactured by Toho Tenax Co., Ltd., average fiber length 6 mm
[Thermoplastic resin (C)]
・ PP: Polypropylene made by Nippon Polypro Co., Ltd. “NOVATEC MA1B” (trade name)

3.9. Evaluation Results In Comparative Example 4, virgin fibers that were not recycled fibers were used as the component (B), and the average fiber length in the test piece of the virgin fibers was 540 nm. According to Comparative Example 4, since the virgin material is used as the component (B), but the component (A) is not added, the bending strength compared to Example 4 or Example 5 using the recycled fiber, Notch-free Charpy impact strength and falling weight impact strength were inferior and poor.

  According to Comparative Example 1, Comparative Example 2, and Comparative Example 6, since component (A) was not included, bending strength, unnotched Charpy impact strength, and falling weight impact strength were inferior and inferior compared to the Examples.

  According to Comparative Example 3 and Comparative Example 5, since the (A) component does not contain an amino group, the (B) component and the (C) component cannot be firmly bonded, and the bending strength, compared to the examples, Notch-free Charpy impact strength and falling weight impact strength were inferior and poor.

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 effects 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)

A polymer (A) having an amino group;
Fiber (B),
A thermoplastic resin (C);
And the fiber (B) is a recycled fiber. A polymer (A) having an amino group;
Fiber (B),
A thermoplastic resin (C);
And the fiber (B) has an average fiber length of 20 μm to 500 μm.   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.