JP2020007648A - Fibrous material and fiber reinforced resin composition - Google Patents

Abstract

To provide a fibrous material that is not too rigid and has good strength and solvent resistance.SOLUTION: Provided is a fibrous material in which a hydroxyl group in cyclodextrin of polyrotaxane in which a straight-chain molecule penetrates a cyclic structure of cyclodextrin and blocking groups are provided at both ends of the straight-chain molecule, and a hydroxyl group of a cellulose fiber having a molecular structure represented by the following formula (I) (in formula (I), n=10 or more and 1000000 or less) are linked by a linker.SELECTED DRAWING: None

Description

  The present invention relates to a fibrous substance and a fiber-reinforced resin composition.

  2. Description of the Related Art Composite materials have been studied as a candidate material for improving the strength and reducing the weight of various products. In recent years, polyrotaxanes having a structure in which cyclic molecules are skewered with linear molecules have been attracting attention. Polyrotaxanes are also referred to as slide ring materials, ring polymers, and ring gels.

  For example, Patent Document 1 discloses a fiber material having a polyrotaxane and fibers. Patent Literature 2 discloses a polymer blend comprising a polyrotaxane and a polymer material.

JP 2008-001997 A JP 2007-092024 A

  In the fiber material described in Patent Literature 1 and the polymer blend described in Patent Literature 2, mixing and compounding of polyrotaxane in the material are attempted. However, as a material, it cannot be said that the performance expected from the molecular structural characteristics of the polyrotaxane has always been sufficiently brought out.

（式（Ｉ）中、ｎ＝１０以上１００００００以下）
が有する水酸基と、
が、リンカーにより結合されている。 One embodiment of the fibrous substance according to the present invention,
A hydroxyl group of the cyclodextrin of the polyrotaxane in which the linear molecule penetrates the cyclic structure of the cyclodextrin and a blocking group is provided at both ends of the linear molecule,
Cellulose fiber having a molecular structure represented by the following formula (I)

(In the formula (I), n = 10 or more and 1,000,000 or less)
Having a hydroxyl group,
Are connected by a linker.

In one embodiment of the fibrous material,
The linker may include a bond selected from an ester bond, a urethane bond, and an amide bond.

In one embodiment of the fibrous material,
The hydroxyl group of the cyclodextrin is unmodified or modified,
A bond derived from one or more of the unmodified hydroxyl group and the modified group may be included in the linker.

（式（ＩＩ）中、−Ｒ^１は、−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_２−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ−（ＣＨ_３）_２、及び、−(ＣＯ−ＣＨ_２−ＣＨ_２−ＣＨ_２−ＣＨ_２−ＣＨ_２）_ｍ−ＯＨ（ｍ＝２０以上１０００以下）から選ばれる基であり、−Ｒ^２は、−Ｈ、−ＯＨ、−ＣＯＯＨ及び−ＮＨ_２から選ばれる基である。）
で表される基になるように変性され、
前記未変性の水酸基及び前記変性基の１つ以上に由来する結合が前記リンカーに含まれることができる。 In one embodiment of the fibrous material,
The hydroxyl group of the cyclodextrin is unmodified,
The following formula (II)

(In the formula (II), -R ¹ _{is, -CH 2 -CH 3, -CH 2} -O-CH 3, -CH 2 -O-CH 2 -CH 3, -CH 2 -O-CH 2 -CH _{2 -CH 3, -CH 2 -O-} CH- (CH 3) 2, _{and, - (CO-CH 2 -CH} 2 -CH 2 -CH 2 -CH 2) m -OH (m = 20 to 1000 ) from a group ^selected, -R 2 is a radical selected -H, -OH, from -COOH and -NH _2.)
Is modified to become a group represented by
A bond derived from one or more of the unmodified hydroxyl group and the modified group may be included in the linker.

In one embodiment of the fibrous material,
The hydroxyl group of the cellulose fiber is unmodified or modified,
A bond derived from one or more of the unmodified hydroxyl group and the modified group may be included in the linker.

（式（ＩＩ）中、−Ｒ^１は、−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_２−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ−（ＣＨ_３）_２、及び、−(ＣＯ−ＣＨ_２−ＣＨ_２−ＣＨ_２−ＣＨ_２−ＣＨ_２）_ｍ−ＯＨ（ｍ＝２０以上１０００以下）から選ばれる基であり、−Ｒ^２は、−Ｈ、−ＯＨ、−ＣＯＯＨ及び−ＮＨ_２から選ばれる基である。）
で表される基になるように変性され、
前記未変性の水酸基及び前記変性基の１つ以上に由来する結合が前記リンカーに含まれ
ることができる。 In one embodiment of the fibrous material,
The hydroxyl group of the cellulose fiber is unmodified,
The following formula (II)

(In the formula (II), -R ¹ _{is, -CH 2 -CH 3, -CH 2} -O-CH 3, -CH 2 -O-CH 2 -CH 3, -CH 2 -O-CH 2 -CH _{2 -CH 3, -CH 2 -O-} CH- (CH 3) 2, _{and, - (CO-CH 2 -CH} 2 -CH 2 -CH 2 -CH 2) m -OH (m = 20 to 1000 ) from a group ^selected, -R 2 is a radical selected -H, -OH, from -COOH and -NH _2.)
Is modified to become a group represented by
A bond derived from one or more of the unmodified hydroxyl group and the modified group may be included in the linker.

In one embodiment of the fibrous material,
The linear molecule may include a polyethylene glycol chain.

In one embodiment of the fibrous material,
The linker is a bond selected from an ester bond and an amide bond, and a hydroxyl group of the cyclodextrin and a hydroxyl group of the cellulose fiber may be modified to a carboxyl group or an aldehyde group.

In one embodiment of the fibrous material,
The linker may include a structure derived from a crosslinking agent.

In one embodiment of the fibrous material,
The crosslinking agent is a compound having two or more isocyanate groups, and a hydroxyl group of the cyclodextrin and a hydroxyl group of the cellulose fiber can react with an isocyanate group of the crosslinking agent to form a urethane bond. .

In one embodiment of the fibrous material,
The cross-linking agent is a compound having two or more hydroxyl groups, and the hydroxyl group of the cyclodextrin and the hydroxyl group of the cellulose fiber are both modified to a carboxyl group or an aldehyde group, and the modified group is used for the crosslinking agent. It can react with a hydroxyl group to form an ester bond.

In one embodiment of the fibrous material,
The cross-linking agent is a compound having two or more amino groups, and the hydroxyl group of the cyclodextrin and the hydroxyl group of the cellulose fiber are both modified to a carboxyl group or an aldehyde group. To form an amide bond.

In one embodiment of the fibrous material,
The cellulose fibers may have an average fiber diameter of 3.0 nm or more and 100.0 μm or less.

One embodiment of the fiber-reinforced resin composition according to the present invention,
One embodiment of the above fibrous material,
A polymer compound;
including.

In one embodiment of the fiber reinforced resin composition,
It can be used for wearable devices, clothing, containers, films, tires, and elastomeric members including belts.

（式（Ｉ）中、ｎ＝１０以上１００００００以下）
高分子化合物又は高分子化合物の前駆体と、
を架橋反応させて得られる。 One embodiment of the fiber-reinforced resin composition according to the present invention,
A cyclic structure of cyclodextrin is penetrated by a linear molecule, and a polyrotaxane having a blocking group provided at both ends of the linear molecule;
A cellulose fiber having a molecular structure represented by the following formula (I):

(In the formula (I), n = 10 or more and 1,000,000 or less)
A polymer compound or a precursor of the polymer compound,
Are subjected to a cross-linking reaction.

In one embodiment of the fiber reinforced resin composition,
It may contain a bond selected from an ester bond, a urethane bond and an amide bond.

In one embodiment of the fiber reinforced resin composition,
The hydroxyl group of the cyclodextrin is unmodified or modified,
One or more of the unmodified hydroxyl group and the modifying group can form the bond.

（式（ＩＩ）中、−Ｒ^１は、−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_２−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ−（ＣＨ_３）_２、及び、−(ＣＯ−ＣＨ_２−ＣＨ_２−ＣＨ_２−ＣＨ_２−ＣＨ_２）_ｍ−ＯＨ（ｍ＝２０以上１０００以下）から選ばれる基であり、−Ｒ^２は、−Ｈ、−ＯＨ、−ＣＯＯＨ及び−ＮＨ_２から選ばれる基である。）
で表される基になるように変性され、
前記未変性の水酸基及び前記変性基の１つ以上が前記結合を形成することができる。 In one embodiment of the fiber reinforced resin composition,
The hydroxyl group of the cyclodextrin is unmodified,
The following formula (II)

(In the formula (II), -R ¹ _{is, -CH 2 -CH 3, -CH 2} -O-CH 3, -CH 2 -O-CH 2 -CH 3, -CH 2 -O-CH 2 -CH _{2 -CH 3, -CH 2 -O-} CH- (CH 3) 2, _{and, - (CO-CH 2 -CH} 2 -CH 2 -CH 2 -CH 2) m -OH (m = 20 to 1000 ) from a group ^selected, -R 2 is a radical selected -H, -OH, from -COOH and -NH _2.)
Is modified to become a group represented by
One or more of the unmodified hydroxyl group and the modifying group can form the bond.

In one embodiment of the fiber reinforced resin composition,
The hydroxyl group of the cellulose fiber is unmodified or modified,
One or more of the unmodified hydroxyl group and the modifying group can form the bond.

（式（ＩＩ）中、−Ｒ^１は、−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_２−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ−（ＣＨ_３）_２、−(ＣＯ−ＣＨ_２−ＣＨ_２−ＣＨ_２−ＣＨ_２−ＣＨ_２）_ｍ−ＯＨ（ｍ＝２０以上１０００以下）から選ばれる基であり、−Ｒ^２は、−Ｈ、−ＯＨ、−ＣＯＯＨ及び−ＮＨ_２から選ばれる基である。）
で表される基になるように変性され、
前記未変性の水酸基及び前記変性基の１つ以上が前記結合を形成することができる。 In one embodiment of the fiber reinforced resin composition,
The hydroxyl group of the cellulose fiber is unmodified,
The following formula (II)

(In the formula (II), -R ¹ _{is, -CH 2 -CH 3, -CH 2} -O-CH 3, -CH 2 -O-CH 2 -CH 3, -CH 2 -O-CH 2 -CH _{2 -CH 3, -CH 2 -O-} CH- (CH 3) 2, - from _{(CO-CH 2 -CH 2 -CH} 2 -CH 2 -CH 2) m -OH (m = 20 to 1,000) a group ^selected, -R 2 is a radical selected -H, -OH, from -COOH and -NH _2.)
Is modified to become a group represented by
One or more of the unmodified hydroxyl group and the modifying group can form the bond.

In one embodiment of the fiber reinforced resin composition,
The linear molecule may include a polyethylene glycol chain.

In one embodiment of the fiber reinforced resin composition,
The cellulose fibers may have an average fiber diameter of 3.0 nm or more and 100.0 μm or less.

In one embodiment of the fiber reinforced resin composition,
It can be used for wearable devices, clothing, containers, films, tires, and elastomeric members including belts.

Schematic diagram of the molecular structure of polyrotaxane. The conceptual diagram of the structure of a fibrous substance. The conceptual diagram of the structure of a fiber reinforced resin composition.

  Hereinafter, some embodiments of the present invention will be described. The embodiment described below describes an example of the present invention. The present invention is not limited to the following embodiments at all, and includes various modifications implemented without departing from the spirit of the present invention. Note that not all of the configurations described below are essential configurations of the present invention.

1. Fibrous substance In the fibrous substance of the present embodiment, the hydroxyl group of the cyclodextrin of the polyrotaxane and the hydroxyl group of the cellulose fiber are linked by a linker.

1.1. Polyrotaxane Polyrotaxane is a compound or chemical substance called a so-called slide ring material in which a linear molecule penetrates a cyclic structure of cyclodextrin, and a blocking group is provided at both ends of the linear molecule.

1.1.1. Cyclodextrin Cyclodextrin is a kind of cyclic oligosaccharide, and is a compound having a cyclic structure in which D-glucose is linked by α-1,4-glycosidic bonds. Cyclodextrin is one in which five or more glucoses are bound. Typically, 6-linked glucose is α-cyclodextrin (cyclohexamylose, α-CD), 7-linked glucose is β-cyclodextrin (cycloheptaamylose, β-CD), 8-linked Is γ-cyclodextrin (cyclooctamylose, γ-CD). In the cyclodextrin of the polyrotaxane of the present embodiment, a ring may be formed by more glucose, and the size of the ring can be selected depending on the type of the linear molecule.

  The cyclodextrin of the polyrotaxane of the present embodiment is preferably selected from α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and derivatives thereof.

  Cyclodextrin has a plurality of glucose units and has many hydroxyl groups. The hydroxyl group of cyclodextrin can become a linker or a part of the linker described below by reacting even if it is not modified. Further, the hydroxyl group of cyclodextrin can be modified, and the modified group reacts to become a linker or a part of the linker described below.

  The hydroxyl group of the cyclodextrin in the polyrotaxane is bonded to the hydroxyl group of the cellulose fiber described later via a linker. One of the hydroxyl groups of cyclodextrin may be bonded to the linker, or a plurality of hydroxyl groups may be bonded to the linker. Further, the hydroxyl group of cyclodextrin may be reacted in an undenatured state and bonded to the linker, or may be reacted after being denatured and bonded to the linker.

  Examples of the mode in which the unmodified hydroxyl group reacts and bonds to the linker include an ester bond and a urethane bond. When an ester bond or a urethane bond is formed, the bond itself may be used as a linker.

  Examples of the mode in which the hydroxyl group of cyclodextrin is modified include an amino group, a carboxyl group, an epoxy group, a vinyl group, a thiol group, and an aldehyde group. Among these, when the amino group is modified and reacted to bond to the linker, for example, an embodiment in which the amino group is bonded to the linker by an amide bond, a urea bond, or the like may be mentioned. In the case where the compound is modified into a carboxyl group and reacted to bond to the linker, for example, an embodiment in which the compound is bonded to the linker by an ester bond may be mentioned. Further, these bonds themselves may serve as a linker.

（式（ＩＩ）中、−Ｒ^１は、−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_２−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ−（ＣＨ_３）_２、及び、−(ＣＯ−ＣＨ_２−ＣＨ_２−ＣＨ_２−ＣＨ_２−ＣＨ_２）_ｍ−ＯＨ（ｍ＝２０以上１０００以下）から選ばれる基であり、−Ｒ^２は、−Ｈ、−ＯＨ、−ＣＯＯＨ及び−ＮＨ_２から選ばれる基である。）
で表される基になるように変性されてもよい。そして、未変性の水酸基及び該変性基の１
つ以上に由来する結合が後述するリンカーに含まれるようにしてもよい。 Further, the hydroxyl group of cyclodextrin is unmodified,
The following formula (II)

(In the formula (II), -R ¹ _{is, -CH 2 -CH 3, -CH 2} -O-CH 3, -CH 2 -O-CH 2 -CH 3, -CH 2 -O-CH 2 -CH _{2 -CH 3, -CH 2 -O-} CH- (CH 3) 2, _{and, - (CO-CH 2 -CH} 2 -CH 2 -CH 2 -CH 2) m -OH (m = 20 to 1000 ) from a group ^selected, -R 2 is a radical selected -H, -OH, from -COOH and -NH _2.)
May be modified so as to become a group represented by And an unmodified hydroxyl group and one of the modified groups
One or more bonds may be included in a linker described below.

  In polyrotaxanes, native or modified cyclodextrin is penetrated by linear molecules in its cyclic structure. The upper limit of the number of cyclodextrin rings penetrated by the linear molecule can be estimated from the relationship between the thickness of the cyclodextrin ring and the length of the linear molecule. For example, when the linear molecule is polyethylene glycol and the cyclic molecule is an α-cyclodextrin molecule, the maximum inclusion amount can be determined experimentally (see, for example, Macromolecules 1993, 26, 5698-5703). . When the upper limit is set to 1, the number of cyclodextrin rings through which the linear molecule penetrates is 0.0001 or more and 0.6 or less, preferably 0.001 or more and 0.5 or less, more preferably 0.1 or less. 005 or more and 0.4 or less.

  If the cyclodextrin ring is within the above range, a sufficient distance for the cyclodextrin ring to move (slide) along the chain of the linear molecule can be obtained. Therefore, a linker is attached to the cyclodextrin of the polyrotaxane. The degree of freedom of sliding and movement of the cellulose fibers bonded through the intermediary can be sufficiently ensured.

1.1.2. Linear Molecule The linear molecule of the polyrotaxane is not particularly limited as long as it is a kind of molecule that can penetrate the cyclodextrin ring. The linear molecule may have a linear molecular chain as a main chain, and may include a branch. Even when the linear molecule contains a branch, the cyclodextrin ring can slide along the molecular chain in the linear molecular chain other than the branched portion. Further, as long as it can penetrate the ring of cyclodextrin, it may contain a side chain (for example, a hydroxyl group of polyvinyl alcohol, a methyl group in polypropylene, a pyrrolidone ring of polyvinyl pyrrolidone).

  Examples of linear molecules include polyvinyl alcohol, polyvinylpyrrolidone, poly (meth) acrylic acid, poly (meth) acrylamide, polymethyl (meth) acrylate, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl methyl ether, polyvinyl formal, Examples thereof include polyvinyl butyral, polystyrene, polyvinyl chloride, polytetrahydrofuran, and polyaniline.

  Examples of the type of the linear molecule include polyolefins such as polyethylene and polypropylene; polydienes such as polyisoprene, polybutadiene and polyisobutylene; polyamides such as nylon; polyamines; polyesters; polycarbonates; Polyimines such as polyethyleneimine; polysiloxanes such as polydimethylsiloxane; polysulfones; polyacetic anhydrides; polyureas; polysulfides; polyphosphazenes; polyketones; polyphenylenes; Celluloses such as hydroxyethylcellulose and hydroxypropylcellulose; starches; caseins; gelatins; polystyrene-based polymers such as acrylonitrile-styrene copolymers; Acrylic resins such as (meth) acrylate copolymers, acrylonitrile-methyl (meth) acrylate copolymers; vinyl chloride-vinyl acetate copolymers; acrylonitrile-butadiene-styrene copolymers (ABS resins); And derivatives, modified products and copolymers thereof may be used.

  Among these, the linear molecule is preferably selected from polyvinyl alcohol, polyethylene oxide, polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene and polypropylene, and more preferably polyethylene glycol. Moreover, it is preferable that at least one part of a linear molecule contains a polyethylene glycol chain.

  The molecular weight of the linear molecule is 10,000 or more, preferably 20,000 or more, and more preferably 35,000 or more.

1.1.3. Blocking Group The blocking group is not particularly limited as long as it is a group capable of exerting an action of preventing the ring of cyclodextrin from leaving the linear molecule. The blocking group is preferably a bulky group that is larger than the inner diameter of the cyclodextrin ring. By disposing the blocking group at the end of the linear molecule, the linear molecule is prevented from falling out of the cyclodextrin. In other words, by disposing the blocking group at the end of the linear molecule, the cyclodextrin hardly comes off from the linear molecule. Note that the blocking group does not need to be disposed at the exact terminal of the linear molecule as long as the cyclodextrin ring can be prevented from leaving the linear molecule.

  Examples of blocking groups include dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, pyrenes, substituted benzenes (substituents such as alkyl, alkyloxy, hydroxy, halogen, cyano, sulfonyl , Carboxyl, amino, phenyl and the like, but are not limited thereto. One or more substituents may be present.), Polynuclear aromatics which may be substituted (as the substituents, those described above) The same may be mentioned, but not limited thereto. One or more substituents may be present.) And steroids. In addition, it is preferable to be selected from dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, and pyrenes, and more preferably adamantane groups or trityl groups.

1.1.4. 1. Concept of Molecular Structure of Polyrotaxane FIG. 1 is a conceptual diagram of the molecular structure of polyrotaxane. As shown in FIG. 1, the polyrotaxane PR includes a cyclodextrin CD, a linear molecule LC, and a blocking group CG. The cyclodextrin ring is penetrated by the linear molecule LC and can move along the molecular chain of the linear molecule. In this example, the blocking group CG is bonded to both ends of the linear molecule, so that the cyclodextrin CD is not released from the linear molecule LC.

  The polyrotaxane PR has a degree of freedom of deformation due to sliding of the cyclodextrin CD along the linear molecule LC, in addition to a degree of freedom of deformation due to expansion and contraction and bending of the linear molecule LC.

  Then, in the fibrous substance of the present embodiment, the cellulose fibers described below are bonded to the cyclodextrin and the linker. Therefore, in addition to the rigidity of the cellulose fiber, the flexibility of the slide of cyclodextrin can be obtained.

1.2. Cellulose fiber Cellulose fiber is a fiber containing cellulose as a main component. Cellulose is a polymer in which β-glucose molecules are linearly polymerized by glycosidic bonds. The cellulose fiber may include a partially non-cellulose molecular structure such as a branched structure, if such a cellulose unit is included. Therefore, cellulose constituting the cellulose fiber has a molecular structure represented by the following formula (I).

（上記式（Ｉ）中、ｎは１０以上１０００００以下の整数を表す。）

(In the above formula (I), n represents an integer of 10 or more and 100,000 or less.)

  As the cellulose fiber, for example, nanofiber, regenerated pulp, pulp and the like can be used. Cellulose fibers are basically in the form of a string or a string, and may be a single independent fiber, or a plurality of fibers intertwined with each other to form a string or a flat string as a whole. It may be in a shape. Further, the cellulose fiber may have a linear shape as a whole, a curved shape, or a contracted shape. The cross-sectional shape of the cellulose fiber is not particularly limited, and may be a circle, an ellipse, a polygon, or a combination thereof. Further, fibrillated fibers or nanofibers (cellulose nanofibers) may be used.

  When the cellulose fiber used in the present embodiment is a single independent fiber, its average diameter (the largest one among the lengths in the direction perpendicular to the longitudinal direction when the cross section is not a circle) Or, assuming a circle having an area equal to the cross-sectional area, the diameter (equivalent circle diameter) of the circle is, on average, 2.0 nm or more and 100.0 μm or less, preferably 3.0 nm or more and 100.0 μm or less. The thickness is more preferably 3.0 nm or more and 10.0 μm or less, and still more preferably 4.0 nm or more and 1.0 μm or less.

  The length of the cellulose fiber used in the present embodiment is not particularly limited, but is a single independent fiber, the length along the longitudinal direction of the fiber is 400.0 nm or more and 5.0 mm or less, preferably, It is 500.0 nm or more and 3.0 mm or less, more preferably 1.0 μm or more and 2.0 mm or less. Note that the length of the cellulose fiber may have a variation (distribution), and for a length of one independent fiber, when a normal distribution is assumed in a distribution obtained by n number of 100 or more, σ may be from 1.0 μm to 1000.0 μm, preferably from 500.0 nmm to 500.0 μm.

  Further, the aspect ratio (the ratio of the length to the diameter) of the cellulose fiber is preferably 100.0 or more, more preferably 200.0 or more, and further preferably 300.0 or more.

  The thickness (diameter) and length of the cellulose fiber can be measured by various optical microscopes, a scanning electron microscope (SEM), a transmission electron microscope, a fiber tester, or the like. In the case of microscopic observation, pretreatment of the observation sample is appropriately performed as necessary, so that cross-section observation and observation in a state where both ends of one independent fiber are pulled so as not to be broken as necessary. And so on.

  When dyeing the cellulose fiber, the type and color of the dye are not limited, and a direct dye, an azoic dye, a sulfur dye, a vat dye, a reactive dye, or the like can be appropriately used. In addition, in this specification, dyeing of a cellulose fiber shall not be considered as modification of the cellulose fiber.

  Cellulose constituting the cellulose fiber has a plurality of glucose units and has many hydroxyl groups. The hydroxyl group of the cellulose constituting the cellulose fiber can become a linker or a part of the linker described below by reacting even if it is not modified. Further, the hydroxyl group of cellulose constituting the cellulose fiber can be modified, and can react with the modified group to become a linker or a part of the linker described below.

  The hydroxyl group of the cellulose constituting the cellulose fiber is bonded to the hydroxyl group of the above-described cyclodextrin of the polyrotaxane via a linker. One of the hydroxyl groups of cellulose constituting the cellulose fiber may be bonded to the linker, or a plurality of hydroxyl groups may be bonded to the linker. Further, the hydroxyl group of the cellulose constituting the cellulose fiber may be reacted in an unmodified state and bonded to the linker, or may be reacted after being modified and bonded to the linker.

  Examples of the mode in which the unmodified hydroxyl group reacts and bonds to the linker include an ester bond and a urethane bond. When forming an ester bond, the ester bond itself may serve as a linker.

  Examples of the mode in which the hydroxyl group of the cellulose constituting the cellulose fiber is modified include an amino group, a carboxyl group, an epoxy group, a vinyl group, a thiol group, and an aldehyde group. Among these, when the amino group is modified to react and bond to the linker, for example, an embodiment in which the compound is bonded to the linker by an amide bond, a urethane bond, a urea bond (urea bond), or the like is given. In the case where the compound is modified into a carboxyl group and reacted to bond to the linker, for example, an embodiment in which the compound is bonded to the linker by an ester bond or the like may be mentioned. Further, these bonds themselves may serve as a linker.

（式（ＩＩ）中、−Ｒ^１は、−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ_２−ＣＨ_２−ＣＨ_３、−ＣＨ_２−Ｏ−ＣＨ−（ＣＨ_３）_２、及び、−(ＣＯ−ＣＨ_２−ＣＨ_２−ＣＨ_２−ＣＨ_２−ＣＨ_２）_ｍ−ＯＨ（ｍ＝２０以上１０００以下）から選ばれる基であり、−Ｒ^２は、−Ｈ、−ＯＨ、−ＣＯＯＨ及び−ＮＨ_２から選ばれる基である。）
で表される基になるように変性されてもよい。
そして、未変性の水酸基及び該変性基の１つ以上に由来する結合がリンカーに含まれてもよい。 Further, the hydroxyl group of the cellulose constituting the cellulose fiber is unmodified,
The following formula (II)

(In the formula (II), -R ¹ _{is, -CH 2 -CH 3, -CH 2} -O-CH 3, -CH 2 -O-CH 2 -CH 3, -CH 2 -O-CH 2 -CH _{2 -CH 3, -CH 2 -O-} CH- (CH 3) 2, _{and, - (CO-CH 2 -CH} 2 -CH 2 -CH 2 -CH 2) m -OH (m = 20 to 1000 ) from a group ^selected, -R 2 is a radical selected -H, -OH, from -COOH and -NH _2.)
May be modified so as to become a group represented by
Then, the linker may include a bond derived from an unmodified hydroxyl group and one or more of the modified groups.

1.3. Linker and Variations thereof In the fibrous substance of the present embodiment, the hydroxyl group of the above-mentioned cyclodextrin of the polyrotaxane and the hydroxyl group of the above-mentioned cellulose constituting the cellulose fiber are bonded by a linker. As described above, the linker can include an ester bond, an amide bond, a urethane bond, a urea bond, and the like, and may be the bond itself. Such a bond may be formed by a reaction in which one or both of the hydroxyl group of cyclodextrin and the hydroxyl group of cellulose are appropriately modified unmodified or modified to an amino group, a carboxyl group, an isocyanate group, or the like.

  Further, for example, the hydroxyl group of the cyclodextrin and the hydroxyl group of the cellulose fiber may be modified and reacted with a carboxyl group or an aldehyde group, and the linker may be a bond selected from an ester bond and an amide bond.

  On the other hand, the linker may be a molecular chain including a bond selected from an ester bond, an amide bond, a urethane bond, and a urea bond. An embodiment in which the linker is composed of a molecular chain containing these bonds corresponds to, for example, a case where the hydroxyl group of cyclodextrin and / or cellulose is modified to a hydroxyalkyl group or a case where the hydroxyl group is modified by caprolactone. Further, the embodiment in which the linker is composed of a molecular chain containing these bonds is, for example, a linker in the case where the hydroxyl groups of cyclodextrin and cellulose are bonded in a denatured or undenatured state, for example, with a cross-linking agent such as diisocyanate. This corresponds to this. When the linker contains a bond selected from an ester bond, a urethane bond and an amide bond, production of a fibrous substance may be facilitated.

  In other words, the hydroxyl group of the cyclodextrin may be unmodified or modified, and the linker may include an unmodified hydroxyl group and a bond derived from one or more of the modified groups. Further, the hydroxyl group of the cellulose fiber may be unmodified or modified, and the linker may include a bond derived from one or more of the unmodified hydroxyl group and the modified group. Further, the linker may include a structure derived from a crosslinking agent. The fibrous substance of the present embodiment may be formed by crosslinking the hydroxyl groups of cellulose and the hydroxyl groups of cyclodextrin using a crosslinking agent.

  The cross-linking agent may be of any type as long as the hydroxyl group of the cyclodextrin and the hydroxyl group of the cellulose fiber are unmodified or modified and can react with the functional group of the cross-linking agent to form a chemical bond. Can be used.

  Specific examples of the crosslinking agent include a compound having two or more isocyanate groups, a compound having two or more hydroxyl groups, and a compound having two or more amino groups. If the cross-linking agent is a compound having two or more isocyanate groups, the hydroxyl group of the cyclodextrin and the hydroxyl group of the cellulose can each react with the isocyanate group of the cross-linking agent to form a urethane bond, and the urethane bond Can be formed. Further, if the crosslinking agent is a compound having two or more hydroxyl groups, the hydroxyl group of the cyclodextrin and the hydroxyl group of the cellulose, both modified by using a carboxyl group or aldehyde group, by using the modified group, the crosslinking agent Can form an ester bond by reacting with a hydroxyl group of the above, and can form a linker containing the ester bond. Furthermore, if the cross-linking agent is a compound having two or more amino groups, the hydroxyl group of the cyclodextrin and the hydroxyl group of the cellulose fiber are both modified to a carboxyl group or an aldehyde group, and the modified group is An amide bond can be formed by reacting with an amino group, and a linker containing an amide bond can be formed.

  The molecular weight of the cross-linking agent and the number of functional groups are not particularly limited, but those having a molecular weight of 100 to 10,000, preferably 200 to 8,000, more preferably 300 to 5,000 can be used. It may be functional or more.

  Further, as another embodiment of the cross-linking agent, for example, cyanuric chloride, trimesoyl chloride, terephthaloyl chloride, epichlorohydrin, dibromobenzene, glutaraldehyde, phenylene diisocyanate, trioleic diisocyanate, divinyl sulfone, 1,1 It may be selected from '-carbonyldiimidazole and alkoxysilanes.

  The length of the linker in the fibrous substance is not particularly limited.For example, when the length of the linker is long, such as when extended with a caprolactone chain as described above, or when the molecular weight of the crosslinking agent is large, In addition, the degree of freedom of deformation due to expansion and contraction of the linker is likely to occur. Therefore, the flexibility of the fibrous substance may be improved in some cases.

1.4. FIG. 2 is a conceptual diagram of the structure of a fibrous substance. As shown in FIG. 2, the fibrous material FM includes a cellulose fiber CF and a cyclodextrin CD of a polyrotaxane PR bonded by a linker LI. The ring of the cyclodextrin CD is penetrated by the linear molecule LC and can move along the molecular chain of the linear molecule. Therefore, in addition to the rigidity of the cellulose fiber CF, the flexibility of the slide of the cyclodextrin CD can be obtained.

1.5. Action and Effect In the fibrous substance of the present embodiment, the cellulose fibers are chemically bonded to the cyclodextrin of the polyrotaxane. Therefore, the cyclodextrin slides along the linear molecule of the polyrotaxane, and thus has a degree of freedom in shape change. That is, when a force (tension and / or stress) is applied to the fibrous material, expansion and contraction by movement of the cyclodextrin is possible. Therefore, the fibrous substance of this embodiment can express the rigidity of the cellulose fiber and the flexibility of the shape change of the polyrotaxane. In addition, since the polyrotaxane is fixed to the cellulose fiber, it is hardly eluted in an organic solvent or the like.

  The fibrous substance of the present embodiment can be suitably used as a filler (reinforcing material) of a polymer material, and for example, can be mixed and kneaded with an appropriate polymer substance to form a fiber reinforced resin.

1.6. Production Example of Fibrous Substance The fibrous substance of the present embodiment can be produced, for example, by preparing a polyrotaxane and reacting the polyrotaxane with cellulose fibers. An example of a fibrous substance will be described below, and an outline of a production method thereof will be described. In the following example, PEG (polyethylene glycol) is used as a linear molecule, α-CD is used as a cyclodextrin, adamantane is used as a blocking group, and diisocyanate is used to form a linker. Not something.

1.6.1. Preparation of polyrotaxane Preparation of PEG-carboxylic acid by TEMPO oxidation of PEG Dissolve PEG, TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy radical) and sodium bromide in water. An aqueous solution of sodium hypochlorite is added to the obtained solution, and the mixture is reacted at room temperature with stirring. As the reaction proceeds, the pH of the system rapidly decreases immediately after the addition, but the system is prepared by adding NaOH so as to keep the pH at 10 to 11. The reaction is terminated by appropriately adding ethanol. Components other than inorganic salts are extracted by extraction with methylene chloride, and methylene chloride is distilled off by an evaporator. After dissolving in warm ethanol, it is stored in a freezer to precipitate PEG-carboxylic acid, that is, PEG in which both ends of PEG are substituted with carboxylic acid (—COOH). The precipitated PEG-carboxylic acid is recovered by centrifugation. This cycle of hot ethanol dissolution-precipitation-centrifugation is appropriately repeated and dried by vacuum drying to obtain PEG-carboxylic acid.

-Mixing of PEG-carboxylic acid and α-CD PEG-carboxylic acid and α-CD are respectively dissolved in separately prepared warm water. Thereafter, the two are mixed and then left standing in a refrigerator. The substance that precipitates in the form of a cream is lyophilized and recovered. The precipitated substance contains a structure in which PEG-carboxylic acid penetrates the α-CD ring.

・ Sequestration using adamantaneamine and BOP reagent reaction system Adamantaneamine, BOP reagent (benzotriazol-1-yl-oxy-tris (dimethylamino) phosphonium hexafluorophosphate) and diisopropylethylamine were dehydrated into dehydrated dimethylformamide. Add the solution dissolved in (DMF) and shake well. Then, it is left still in the refrigerator. Thereafter, methanol is added, and the mixture is stirred, centrifuged, and the supernatant is removed. Next, a mixed solution of DMF / methanol = 1: 1 is added, and the same operation is performed an appropriate number of times. Further, the same operation is repeated an appropriate number of times using methanol, and the obtained precipitate is dried in vacuum and then dissolved in dimethylsulfoxide (DMSO). This solution is dropped into pure water to precipitate polyrotaxane. The precipitated polyrotaxane is collected by centrifugation and dried in vacuum. If necessary, the same reprecipitation operation is performed to obtain a polyrotaxane.

  The length of the linear molecule of polyrotaxane and the number of cyclodextrins can be adjusted by, for example, the charged composition.

1.6.2. Denaturation of Hydroxyl Group of Cyclodextrin ・ Oxymethylation of α-CD The polyrotaxane obtained above is dissolved in dehydrated DMSO, and a methanol solution of sodium methoxide (equivalent to the equivalent amount of hydroxyl group of α-CD molecule in polyrotaxane) After adjusting the amount), methanol was distilled off under reduced pressure. After adding methyl iodide and stirring, the reaction solution is diluted with purified water, and the diluted solution is dialyzed with a dialysis tube under flowing tap water. Further, dialysis is performed an appropriate number of times in purified water and freeze-dried to obtain a methylated polyrotaxane in which a part of the OH groups of α-CD is substituted with OCH ₃ groups.

1.6.3. Preparation of fibrous material Cellulose fibers are dispersed in an aqueous NaOH solution. The above-mentioned methylated polyrotaxane is added to and dissolved in this solution. An example of the fibrous substance of the present embodiment can be obtained by adding divinyl sulfone to the mixture and allowing the mixture to stand.

  The length of the linker of the fibrous substance, the type of bond between the cellulose fiber and the cyclodextrin, the number (density), and the like can be adjusted by, for example, the charge composition.

2. Fiber reinforced resin composition 2.1. First Embodiment The fiber reinforced resin composition of the present embodiment contains the above-mentioned fibrous substance and a polymer compound. The fiber-reinforced resin composition of the first embodiment can be obtained by mixing the above-mentioned fibrous substance and a polymer compound. The method of mixing is not particularly limited, and methods such as kneading and solution blending can be used. Further, a fiber-reinforced resin composition may be obtained by mixing a fibrous substance and a monomer of a polymer compound and polymerizing the monomer.

  The polymer compound is not particularly limited, and any of a thermoplastic resin and a thermosetting resin can be used. Further, the content of the fibrous substance in the fiber reinforced resin composition is not limited. Further, the fiber reinforced resin composition can appropriately contain an additive that is blended with a general polymer compound.

Specific examples of the polymer compound include ethylene-propylene-diene terpolymer rubber (EP
DM), acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber (CR), chlorosulfonated polyethylene rubber (CSM), ethylene-propylene copolymer rubber (EPM), acrylic rubber (ACM), hydrin rubber, styrene-butadiene copolymer Polymerized rubber (SBR), isobutylene-isoprene copolymer rubber (IIR), natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), urethane rubber, silicone rubber, fluorine rubber, and the like. . These may be used alone or a plurality of them may be used as a mixture.

  Further, specific examples of the polymer compound include polyvinyl chloride resin (PVC), polyethylene resin (PE), polypropylene resin (PP), polyvinylidene chloride resin, polystyrene resin (PS), polyvinyl alcohol resin (PVA), and polyvinyl acetate. Resin (PVAc), acrylic resin, ethylene-vinyl acetate copolymer resin (EVA), polyester, polyamide (PA), polylactic acid (PLA) and the like. These may be used alone or a plurality of them may be used as a mixture. In addition, a thermoplastic elastomer can be used, and when a watch band or the like is formed, the thermoplastic elastomer is more preferable in terms of moldability and low irritation.

  The mixing method is not particularly limited, and examples thereof include a method of kneading using an open roll, a Banbury mixer, a kneader, a screw extruder, and the like.

  Although not shown, the fiber-reinforced resin composition of the first embodiment has a structure in which the above-mentioned fibrous substance is dispersed in a polymer compound. The type and blending amount of the fibrous substance are arbitrary. For example, the fibrous substance is 0.1% by mass or more and less than 50% by mass, preferably 0.3% by mass, based on the entire fiber-reinforced resin composition. Not less than 20% by mass, more preferably not less than 0.5% by mass and not more than 10% by mass.

  Since the fiber-reinforced resin composition of the first embodiment contains the above-described fibrous substance, the rigidity can be increased as compared with a single polymer compound. In addition, it is possible to prevent the impact resistance from being reduced by the slide of the cyclodextrin of the polyrotaxane. In addition, since the polyrotaxane is bonded to the cellulose fiber, elution of the polyrotaxane and swelling of the composition are suppressed, and the solvent is excellent.

  In addition, since the fiber-reinforced resin composition of the first embodiment can be produced only by mixing a fibrous substance and a polymer compound, for example, a cross-linking reaction or the like during mixing is unnecessary, and the time required for production is reduced. Thus, manufacturing costs can be reduced.

  FIG. 3 is a conceptual diagram of the structure of the fiber-reinforced resin composition of the first embodiment. In the fiber reinforced resin composition FR, the fibrous substance FM has, as shown in FIG. 3, a cellulose fiber CF and a cyclodextrin CD of a polyrotaxane PR bonded by a linker LI. And it is dispersed in the polymer compound PC. In FIG. 3, the linker LI is schematically depicted by a solid line, and the polymer compound PC is schematically depicted by a broken line.

  In the fiber reinforced resin composition of the first embodiment, it is expected that the cellulose fiber CF increases the strength and rigidity, and the polyrotaxane PR increases the flexibility. Further, in the fiber reinforced resin composition of the first embodiment, since the polyrotaxane PR is bonded to the cellulose fibers CF, solvent resistance can be ensured.

2.2. Second Embodiment The fiber reinforced resin composition of the second embodiment is obtained by performing a cross-linking reaction between the above-mentioned polyrotaxane, the above-mentioned cellulose fiber, and a polymer compound or a precursor of a polymer compound.

  The fiber reinforced resin composition of the second embodiment has a structure in which cyclodextrin of polyrotaxane, cellulose constituting cellulose fibers, and a polymer compound or a polymer precursor are crosslinked by a crosslinking agent. The fiber reinforced resin composition of the second embodiment is different from the fiber reinforced resin composition of the first embodiment in that a linker other than a linker connecting cyclodextrin and cellulose is included. That is, the fiber-reinforced resin composition of the second embodiment includes a linker for connecting cyclodextrin and cellulose, a linker for connecting cyclodextrins, a linker for connecting cellulose, and a linker for connecting cyclodextrin and a polymer compound. And a linker for connecting cellulose and the polymer compound, a linker for connecting the polymer compounds, and the like.

  Also in the second embodiment, the hydroxyl group of cyclodextrin and the hydroxyl group of cellulose may be unmodified or modified. Further, the polymer compound may include a group capable of reacting with a hydroxyl group or a modifying group, or may include a group capable of reacting with a functional group of a crosslinking agent.

  The fiber reinforced resin composition of the second embodiment has a feature that it is obtained by performing a cross-linking reaction between a polyrotaxane, the above-described cellulose fiber, and a polymer compound or a precursor of a polymer compound. There are many objects to which the cross-linking agent binds. Therefore, the structure of the obtained composition is very complicated. Therefore, it is difficult to express by a structure using a general formula or the like. In addition, since it is difficult to represent the composition, the characteristics of the composition may be various. In addition, when the crosslinking reaction is performed, if the mixing ratio and the reaction conditions are changed, the characteristics of the obtained composition can be significantly changed. It is difficult to express the fiber reinforced resin composition of the second embodiment by characteristics. That is, it is more practical to specify the fiber-reinforced resin composition according to the second embodiment by a process (production method) for obtaining the composition than to directly specify the structure or properties.

  In the fiber reinforced resin composition of the second embodiment, the fibrous substance, the cellulose fiber, and the cyclodextrin of the polyrotaxane are mutually or randomly bonded. Each component is dispersed in a polymer compound.

  Also in the fiber reinforced resin composition of the second embodiment, the action of the cellulose fiber CF to increase the strength and rigidity and the effect of the polyrotaxane PR to increase the flexibility can be expected. Further, also in the fiber reinforced resin composition of the second embodiment, solvent resistance can be ensured because the polyrotaxane PR is bonded to other components.

  Each of the fiber-reinforced resin compositions of the first embodiment and the second embodiment is, for example, a wearable device such as a watch; a belt; a bedding such as a mattress, a mattress, a pillow; a seat cushion, a handle, a headrest, an armrest, and a vibration damping material. , Floor mats, tires, belts, etc., automotive parts, aerospace parts; flooring, wallpaper, packing, etc., building materials; chairs, chairs, sofas, cushions, etc., furniture; packing materials; films; containers; Grips for tennis rackets, etc., protectors (snowboards, bicycles, etc.), inner helmets (skis, snowboards, motor sports, bicycles, etc.), shoe soles, insoles, golf balls and other sporting goods; grips for pens, underwear, Cosmetic puffs, mannequins, daily necessities such as paints (inks), toys, clothing; Packaging materials, packing, electronic equipment members such as damping material, can be suitably used, for example. In addition, in the fiber reinforced resin compositions of the first and second embodiments, since the polyrotaxane is bonded to the cellulose fiber or the polymer compound, elution of the components due to sweat or an organic solvent is suppressed. Therefore, of these uses, it can be particularly suitably used for wearable devices.

3. EXAMPLES Hereinafter, embodiments of the present invention will be described more specifically with reference to Examples, but the present embodiment is not limited to these Examples. Hereinafter, “parts” and “%” are unless otherwise specified.
It is based on mass.

3.1. Example 1 (fibrous substance)
As the polyrotaxane, a product of Celum Superpolymer SH series manufactured by Advanced Soft Materials Co., Ltd. having polyethylene glycol as a linear molecule, cyclodextrin modified with caprolactone as a cyclodextrin, and an adamantane group as a blocking group was used. As the cellulose fiber, a cellulose nanofiber aqueous dispersion (manufactured by Chuetsu Pulp) was used. Water was removed from the aqueous cellulose nanofiber dispersion by solvent replacement and dispersed in THF. The polyrotaxane was dissolved in diisobutyl ketone, and the cellulose nanofiber THF dispersion was added to this solution while stirring. Heat to 70 ° C. to remove THF. To this solution was added a blocked isocyanate as a crosslinking agent, and the mixture was heated and stirred at 160 ° C. By removing the solvent and purifying, an elastic fiber (fibrous substance) in which the cellulose fiber and the polyrotaxane were linked by a linker having a urethane bond was obtained.

3.2. Example 2 (fibrous substance)
As the polyrotaxane, one having a linear molecule, polyethylene glycol as a linear molecule, cyclodextrin modified with caprolactone as caprolactone, and an adamantane group as a blocking group, of the SELM SUPERPOLYMER SH series manufactured by Advanced Soft Materials was used. As the cellulose fiber, a carboxylated cellulose nanofiber aqueous dispersion (manufactured by Daiichi Kogyo Seiyaku) oxidized by TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) was used. The aqueous dispersion of the carboxylated cellulose nanofiber was replaced with dimethylformamide solvent and added to butyl acetate with 2-hydroxypropylated adamantane polyrotaxane-graft-polycaprolactone dissolved therein with stirring. The mixture was further heated and stirred at 100 ° C. Then, the solvent was removed and purification was performed to obtain stretchable fiber (fibrous substance) in which cellulose fiber and polyrotaxane were bound by a linker having an ester bond.

3.3. Example 3 (fibrous substance)
As the polyrotaxane, one having a linear molecule, polyethylene glycol as a linear molecule, cyclodextrin modified with caprolactone as caprolactone, and an adamantane group as a blocking group, of the SELM SUPERPOLYMER SH series manufactured by Advanced Soft Materials was used. Then, polyrotaxane was oxidized with a TEMPO oxidation catalyst, and caprolactone having a terminal substituted with carboxylic acid was used. As the cellulose fiber, a carboxylated cellulose nanofiber aqueous dispersion (manufactured by Daiichi Kogyo Seiyaku) oxidized by TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) was used.

  The polyrotaxane and the cellulose fiber were dispersed in water, and ethylene glycol was added as a crosslinking agent, and the mixture was heated and stirred at 100 ° C. By removing and purifying ethylene glycol unreacted with water, a stretchable fiber (fibrous substance) in which cellulose fiber and polyrotaxane were ester-bonded was obtained.

3.4. Pellets and watch bands The stretchable fibers (fibrous substances) of Examples 1 to 3 were added to a thermoplastic elastomer TPSiV4000-60A (urethane elastomer) provided by Dow Corning Toray Co., Ltd. in an amount of 3% by mass using a twin-screw kneader. And kneaded to obtain pellets. The kneading temperature was 190 ° C to 220 ° C. The obtained pellets were evaluated for strength, rigidity and impact resistance. In addition, the watch was molded into a watch band shape by an injection molding machine and used for a solvent resistance test.

3.5. Comparative Example 1 to Comparative Example 3
In Comparative Example 1, a pellet and a watch band were formed in the same manner as in Example 4 except that only TPSiV4000-60A was used. In Comparative Example 2, carboxylated cellulose nanofiber powder oxidized by TEMPO in a twin-screw kneader was added to TPSiV4000-60A in an amount of 3% by mass and kneaded to obtain pellets, in the same manner as in Example 4. , Pellets and watch bands.

  In Comparative Example 3, 3% by mass of carboxylated cellulose nanofiber powder oxidized by TEMPO with a twin-screw kneader in TPSiV4000-60A, and polyethylene glycol as a linear molecule of Cell Superpolymer SH series, Pellets and watch bands were formed in the same manner as in Example 4 except that cyclodextrin modified with caprolactone as a dextrin and that having an adamantane group as a blocking group were added and kneaded to obtain pellets.

3.6. Example 4
As the polyrotaxane, one having a linear molecule, polyethylene glycol as a linear molecule, cyclodextrin modified with caprolactone as caprolactone, and an adamantane group as a blocking group, of the SELM SUPERPOLYMER SH series manufactured by Advanced Soft Materials was used. As the cellulose fiber, a cellulose nanofiber aqueous dispersion (manufactured by Chuetsu Pulp) was used.

  The resin used was a pellet of a thermoplastic elastomer TPSiV4000-60A (urethane elastomer) provided by Dow Corning Toray. An aqueous dispersion of cellulose nanofibers was sprayed on the pellets, and the water was dried at 50 ° C. The amount of the cellulose nanofiber added was 1% by mass based on the urethane elastomer. 1% by mass of polyrotaxane was added to the urethane elastomer of the pellet. Further, 0.01% by mass of a blocked isocyanate (manufactured by Meisei Chemical Industry) and 0.1% by mass of bismuth carboxylate (manufactured by Kusumoto Kasei) were added to the urethane elastomer. Then, the mixture was kneaded at 190 ° C. using a twin-screw kneader, and the kneading and the crosslinking reaction were simultaneously performed to obtain pellets for molding.

3.7. Example 5
As the polyrotaxane, a linear molecule, a cyclodextrin obtained by modifying a polyethylene glycol of the SELM SUPERPOLYMER SH series manufactured by Advanced Soft Materials with a force prolactone, and a compound having an adamantane group as a blocking group were used. As the cellulose fiber, a cellulose nanofiber aqueous dispersion (manufactured by Chuetsu Pulp) was used. The resin used was a pellet of a thermoplastic elastomer TPSiV4000-60A (urethane elastomer) provided by Dow Corning Toray.

  An aqueous dispersion of cellulose nanofibers was sprayed on the pellets, and the water was dried at 50 ° C. The amount of the cellulose nanofiber added was 1% by mass based on the urethane elastomer. 1% by mass of polyrotaxane was added to the urethane elastomer of the pellet. Further, hexanediol was added in an amount of 0.01% by mass based on the urethane elastomer, and 0.1% by mass of an organic zirconium compound (manufactured by Matsumoto Chemical). Then, the mixture was kneaded at 190 ° C. using a twin-screw kneader, and the kneading and the crosslinking reaction were simultaneously performed to obtain pellets for molding.

3.8. Pellets and watch bands The pellets for molding of Examples 4 and 5 were formed into a watch belt shape by an injection molding machine and used in a solvent resistance test.

3.9. Comparative Examples 4 to 6
In Comparative Example 4, a watch band was formed using an injection molding machine in the same manner as in Example 5 except that only TPSiV4000-60A was used. In Comparative Example 5, 3% by mass of carboxylated cellulose nanofiber powder oxidized by TEMPO with a twin-screw kneader was added to TPSiV4000-60A, and the mixture was kneaded to obtain a pellet, in the same manner as in Example 4. , Pellets and watch bands.

  In Comparative Example 6, 3% by mass of carboxylated cellulose nanofiber powder oxidized by TEMPO with a twin-screw kneader in TPSiV4000-60A, and polyethylene glycol, cycloalkyl as a linear molecule of Cel super polymer SH series. Pellets and watch bands were formed in the same manner as in Example 4 except that cyclodextrin modified with caprolactone as a dextrin and one having an adamantane group as a blocking group were used, and no blocked isocyanate and bismuth carboxylate were added.

3.10. Evaluation method The evaluation method was as follows.
-Strength and rigidity The strength and rigidity of the material of each example were evaluated according to JIS K6251. A tensile test was performed, and the maximum stress was defined as strength (unit: MPa), and the elastic modulus was defined as rigidity (unit: MPa).
-Impact resistance The impact resistance of the material of each example was evaluated according to JIS K7111. A Charpy impact test with a notch was performed, and both ends of the test piece were fixed. The opposite side of the notch was evaluated by breaking the test piece with a hammer in a high-speed three-point bending mode. Evaluation was made by dividing the impact energy by the cross-sectional area of the test piece (unit: kJ / m ² ).
-Solvent resistance The solvent resistance of the materials of each example was evaluated according to JIS K6258. An immersion test was performed to evaluate the appearance (color change), dimensions, strength, and dissolution.

3.11. Evaluation criteria The evaluation criteria were as follows.
With respect to Examples 1 to 3 and Comparative Examples 1 to 3, based on the evaluation results of Comparative Example 1, the case where the strength was not decreased from Comparative Example 1 was “A”, and the case where the strength was decreased was “B”. Regarding the impact resistance, "A" indicates a case where there is no decrease from Comparative Example 1, and "B" indicates a case where it does. Regarding the stiffness, "A" was given when there was no increase of 50% or more compared to Comparative Example 1, and "B" was given when the increase was 50% or more.

  Regarding the solvent resistance, in each example, "A" was given when the color change by colorimetry before and after immersion was not more than 10%, and "B" was given when the color change was 10% or more. The case where the dimension did not change by 10% or more before and after the immersion was “A”, and the case where the size changed by 10% or more was “B”. Furthermore, if the strength after immersion did not decrease by 10% or more compared to before immersion, it was defined as "A", and if it decreased by 10% or more, it was defined as "B". In the dissolution test, the sample that was eluted when immersed in water and an organic solvent, respectively, was rated "B", and the sample that was not eluted was rated "A".

  Regarding Examples 4 and 5, and Comparative Examples 4 to 6, based on the evaluation result of Comparative Example 4, the case where the strength was not decreased from Comparative Example 4 was “A”, and the case where the strength was decreased was “B”. Regarding the impact resistance, “A” indicates a case where there is no decrease compared to Comparative Example 4, and “B” indicates a case where it has decreased. Regarding the stiffness, “A” was given when there was no increase of 50% or more compared to Comparative Example 4, and “B” was given when there was an increase of 50% or more.

  Regarding the solvent resistance, in each example, "A" was given when the color change by colorimetry before and after immersion was not more than 10%, and "B" was given when the color change was 10% or more. The case where the dimension did not change by 10% or more before and after the immersion was “A”, and the case where the size changed by 10% or more was “B”. Furthermore, if the strength after immersion did not decrease by 10% or more compared to before immersion, it was defined as "A", and if it decreased by 10% or more, it was defined as "B". In the dissolution test, the sample that was eluted when immersed in water and an organic solvent, respectively, was rated "B", and the sample that was not eluted was rated "A".

3.12. Evaluation results Table 1 shows the evaluation results.

3.13. Summary of Results The compositions of Examples 1 to 3 containing the fibrous substance of the present invention had improved rigidity, strength, and impact resistance as compared with the composition of Comparative Example 1 not containing this. Further, the compositions of Examples 1 to 3 were superior in rigidity and impact resistance as compared with Comparative Example 2 containing cellulose fibers. Further, the compositions of Examples 1 to 3 were superior in solvent resistance as compared with Comparative Example 3 containing a cellulose fiber and a polyrotaxane not bonded by a linker. Furthermore, it was found that the compositions of Examples 1 to 3 did not easily decrease impact resistance despite having high rigidity.

  From these results, when the fibrous substance according to the present invention is mixed with a polymer compound, it is possible to improve mechanical properties and ensure solvent resistance. From these results, it was found that the fiber reinforced resin composition according to the present invention has excellent mechanical properties and excellent solvent resistance.

  The compositions of Examples 4 and 5, which are the fiber-reinforced resin compositions of the present invention, have improved rigidity, strength and impact resistance as compared with the composition of Comparative Example 4. Further, the compositions of Examples 4 and 5 were superior in mechanical properties as compared with Comparative Example 5 containing cellulose fibers. Furthermore, the compositions of Examples 4 and 5 were superior in solvent resistance as compared with Comparative Example 6 which contained a polyrotaxane which was not bonded to the composition because no crosslinking agent was used. Furthermore, it was also found that the compositions of Examples 4 and 5 had a high rigidity, but did not easily lower the impact resistance.

  The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the invention includes configurations substantially the same as the configurations described in the embodiments (for example, a configuration having the same function, method, and result, or a configuration having the same object and effect). Further, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. Further, the invention includes a configuration having the same operation and effect as the configuration described in the embodiment or a configuration capable of achieving the same object. The invention also includes a configuration in which a known technique is added to the configuration described in the embodiment.

PR: polyrotaxane, LC: linear molecule, CD: cyclodextrin, CG: blocking group,
FM: fibrous substance, CF: cellulose fiber, LI: linker, FR: fiber-reinforced resin composition, PC: polymer compound

Claims (24)

A hydroxyl group of the cyclodextrin of the polyrotaxane in which the linear molecule penetrates the cyclic structure of the cyclodextrin and a blocking group is provided at both ends of the linear molecule,
Cellulose fiber having a molecular structure represented by the following formula (I)

(In the formula (I), n = 10 or more and 1,000,000 or less)
Having a hydroxyl group,
Are linked by a linker. In claim 1,
The fibrous substance, wherein the linker includes a bond selected from an ester bond, a urethane bond, and an amide bond. In claim 1 or claim 2,
The hydroxyl group of the cyclodextrin is unmodified or modified,
A fibrous substance, wherein a bond derived from one or more of the unmodified hydroxyl group and the modified group is included in the linker. In claim 3,
The hydroxyl group of the cyclodextrin is unmodified,
The following formula (II)

(In the formula (II), -R ¹ _{is, -CH 2 -CH 3, -CH 2} -O-CH 3, -CH 2 -O-CH 2 -CH 3, -CH 2 -O-CH 2 -CH _{2 -CH 3, -CH 2 -O-} CH- (CH 3) 2, _{and, - (CO-CH 2 -CH} 2 -CH 2 -CH 2 -CH 2) m -OH (m = 20 to 1000 ) from a group ^selected, -R 2 is a radical selected -H, -OH, from -COOH and -NH _2.)
Is modified to become a group represented by
A fibrous substance, wherein a bond derived from one or more of the unmodified hydroxyl group and the modified group is included in the linker. In any one of claims 1 to 4,
The hydroxyl group of the cellulose fiber is unmodified or modified,
A fibrous substance, wherein a bond derived from one or more of the unmodified hydroxyl group and the modified group is included in the linker. In claim 5,
The hydroxyl group of the cellulose fiber is unmodified,
The following formula (II)

(In the formula (II), -R ¹ _{is, -CH 2 -CH 3, -CH 2} -O-CH 3, -CH 2 -O-CH 2 -CH 3, -CH 2 -O-CH 2 -CH _{2 -CH 3, -CH 2 -O-} CH- (CH 3) 2, _{and, - (CO-CH 2 -CH} 2 -CH 2 -CH 2 -CH 2) m -OH (m = 20 to 1000 ) from a group ^selected, -R 2 is a radical selected -H, -OH, from -COOH and -NH _2.)
Is modified to become a group represented by
A fibrous substance, wherein a bond derived from one or more of the unmodified hydroxyl group and the modified group is included in the linker. In any one of claims 1 to 6,
The fibrous substance, wherein the linear molecule includes a polyethylene glycol chain. In any one of claims 1 to 7,
The fibrous substance, wherein the linker is a bond selected from an ester bond and an amide bond, and a hydroxyl group of the cyclodextrin and a hydroxyl group of the cellulose fiber are modified to a carboxyl group or an aldehyde group. In any one of claims 1 to 7,
The fibrous substance, wherein the linker includes a structure derived from a crosslinking agent. In claim 9,
The cross-linking agent is a compound having two or more isocyanate groups, and a hydroxyl group of the cyclodextrin and a hydroxyl group of the cellulose fiber respectively react with an isocyanate group of the cross-linking agent to form a urethane bond. material. In claim 9,
The cross-linking agent is a compound having two or more hydroxyl groups, and the hydroxyl group of the cyclodextrin and the hydroxyl group of the cellulose fiber are both modified to a carboxyl group or an aldehyde group, and the modified group is used for the crosslinking agent. A fibrous substance that has reacted with hydroxyl groups to form an ester bond. In claim 9,
The cross-linking agent is a compound having two or more amino groups, and the hydroxyl group of the cyclodextrin and the hydroxyl group of the cellulose fiber are both modified to a carboxyl group or an aldehyde group. A fibrous substance which has reacted with an amino group of the above to form an amide bond. In any one of claims 1 to 12,
The fibrous substance, wherein the cellulose fiber has an average fiber diameter of 3.0 nm or more and 100.0 μm or less. A fibrous substance according to any one of claims 1 to 13,
A polymer compound;
A fiber-reinforced resin composition comprising: In claim 14,
A fiber-reinforced resin composition used for an elastomer member including a wearable device, clothing, a container, a film, a tire, and a belt. A cyclic structure of cyclodextrin is penetrated by a linear molecule, and a polyrotaxane having a blocking group provided at both ends of the linear molecule;
A cellulose fiber having a molecular structure represented by the following formula (I):

(In the formula (I), n = 10 or more and 1,000,000 or less)
A polymer compound or a precursor of the polymer compound,
And a fiber-reinforced resin composition obtained by a crosslinking reaction. In claim 16,
A fiber-reinforced resin composition containing a bond selected from an ester bond, a urethane bond and an amide bond. In claim 17,
The hydroxyl group of the cyclodextrin is unmodified or modified,
A fiber-reinforced resin composition in which one or more of the unmodified hydroxyl group and the modified group form the bond. In claim 18,
The hydroxyl group of the cyclodextrin is unmodified,
The following formula (II)

(In the formula (II), -R ¹ _{is, -CH 2 -CH 3, -CH 2} -O-CH 3, -CH 2 -O-CH 2 -CH 3, -CH 2 -O-CH 2 -CH _{2 -CH 3, -CH 2 -O-} CH- (CH 3) 2, _{and, - (CO-CH 2 -CH} 2 -CH 2 -CH 2 -CH 2) m -OH (m = 20 to 1000 ) from a group ^selected, -R 2 is a radical selected -H, -OH, from -COOH and -NH _2.)
Is modified to become a group represented by
A fiber-reinforced resin composition in which one or more of the unmodified hydroxyl group and the modified group form the bond. In claim 18 or claim 19,
The hydroxyl group of the cellulose fiber is unmodified or modified,
A fiber-reinforced resin composition in which one or more of the unmodified hydroxyl group and the modified group form the bond. In claim 20,
The hydroxyl group of the cellulose fiber is unmodified,
The following formula (II)

(In the formula (II), -R ¹ _{is, -CH 2 -CH 3, -CH 2} -O-CH 3, -CH 2 -O-CH 2 -CH 3, -CH 2 -O-CH 2 -CH _{2 -CH 3, -CH 2 -O-} CH- (CH 3) 2, - from _{(CO-CH 2 -CH 2 -CH} 2 -CH 2 -CH 2) m -OH (m = 20 to 1,000) a group ^selected, -R 2 is a radical selected -H, -OH, from -COOH and -NH _2.)
Is modified to become a group represented by
A fiber-reinforced resin composition in which one or more of the unmodified hydroxyl group and the modified group form the bond. In any one of claims 16 to 21,
The fiber-reinforced resin composition, wherein the linear molecule includes a polyethylene glycol chain. In any one of claims 16 to 22,
The fiber reinforced resin composition, wherein the cellulose fiber has an average fiber diameter of 3.0 nm or more and 100.0 μm or less. In any one of claims 16 to 23,
A fiber-reinforced resin composition used for an elastomer member including a wearable device, clothing, a container, a film, a tire, and a belt.

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