JP2021088686A - Polymer complex including polymer and fiber structure - Google Patents

Abstract

To provide a functional polymer complex having all of flexibility, elasticity, durability, strength, and protection performance.SOLUTION: A polymer complex has a polymer comprising a host group-containing monomer and a guest group-containing monomer and a fiber structure, satisfying 2<Sx/Sy [cutting power ratio] (formula 1) and 2<Ex/Ey [elongation ratio] (formula 2) or 2<Ey/Ex [elongation ratio] (formula 3).SELECTED DRAWING: None

Description

The present invention relates to a polymer complex comprising a polymer and a fibrous structure.

Conventionally, a composite (functional material) having light weight, flexibility, elasticity, high strength, durability and the like has been required. In particular, the development of complexes used as functional materials in various fields is required.

Previous examples of such composites include flexible silicone resins, lightweight and high-strength carbon fiber reinforced plastics (CFRPs), common flexible polymers and high-strength fiber composites, or chemicals. Since the structure has a reversible bond and can be self-repaired, a self-repairing material having excellent durability has been proposed.

For example, in Patent Document 1 (Re-Table 2016-006413), in order to realize self-repairing property of repairing scratches and the like caused by external factors to the original state, a cyclic molecule of a polyrotaxane molecule and this cyclic molecule are used. A polymer material having a crosslinked structure in which polymer molecules other than polyrotaxane molecules are crosslinked via reversible bonds has been proposed.

Further, in Patent Document 2 (Japanese Unexamined Patent Publication No. 2016-186143), a fiber structure such as a knitted fabric having high strength, folding resistance, and light weight using a high-strength spun yarn, and a protective material made of these are described. To provide, woven fabrics using crimped yarns of polyparaphenylene terephthalamide filaments have been proposed.

In Patent Document 3 (Japanese Patent Laid-Open No. 2009-535525), the fibers of the fabric have a very low elongation rate in the machine direction and can be stretched in the lateral direction of the machine with a relatively weak force. Proposed non-woven fabrics are arranged in the fiber direction parallel to the machine direction or forming an angle within ± 45 °.

In Patent Document 4 (Japanese Patent Laid-Open No. 2017-513737), an amphoteric polymer electrolyte (PA) hydrogel realizes abrasion resistance, prevents rejection from the human body, and realizes a high load. To this end, composite materials with fabrics and PA hydrogels have been proposed.

However, there is still a demand for the development of a complex having light weight, flexibility, elasticity (flexibility), high strength, durability and the like.

Re-table 2016/006413 Publication Japanese Unexamined Patent Publication No. 2016-186143 Special Table 2009-535525 Publication Special Table 2017-531737 Publication No.

The present invention proposes a polymer complex that satisfies lightness, flexibility, elasticity (flexibility), high strength, and durability.

The present invention proposes a polymer complex composed of a specific polymer and a fiber structure.

[One aspect of the present invention]
The present invention can propose the following as one aspect thereof.
[1] A polymer complex
It is equipped with a polymer and a fiber structure.
A polymer complex in which the polymer is composed of a host group-containing monomer and a guest group-containing monomer.
[2] The host group may have a substituent, such as cyclodextrin, calixarene, crown ether, cyclophane, cucurbituril, and derivatives thereof, and one or a combination of two or more thereof. ,
The guest group is one or a combination of two or more selected from alkyl groups, cycloalkyl groups, aryl groups, and arylalkyl groups, which may have substituents;
The polymer composite according to [1], wherein the monomer in the host group-containing monomer or the monomer in the guest group-containing monomer is a vinyl-based monomer.
[3] The host group-containing monomer is a polymerizable monomer represented by the following formula (1), or
The polymer complex according to [1], wherein the guest group-containing monomer is a polymerizable monomer represented by the following formula (2).
[In the above formula (1),
Q is O or NH,
CD is cyclodextrin,
^Ra is a hydrogen atom or a methyl group. ]
[In the above equation (2),
A is an aryl group which may have a substituent, C (O) OR1 or C (O) NHR1.
R1 is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an arylalkyl group which may have a substituent.
R ^b is a hydrogen atom or a methyl group. ]
[4] The incision force and the elongation rate of the polymer composite each have anisotropy in the horizontal direction (X direction) of the polymer composite and in the direction perpendicular to the X direction (Y direction). The polymer composite according to any one of [1] to [3].
[5] The incision force Sx in the X direction and the incision force Sy in the Y direction satisfy the following (Equation 1).
2 <Sx / Sy (Equation 1)
[In Equation 1, Sx and Sy are values measured by a measuring method based on ISO 13997 (JIS T 8052)].
When the polymer complex was cut out to 50 mm along the X direction, 10 mm in the Y direction, and 1 mm in thickness and subjected to a tensile test in the X direction, the elongation rate Ex in the X direction at a stress of 0.1 MPa. And then
When the polymer composite was cut out to 50 mm along the Y direction, 10 mm in the X direction, and 1 mm in thickness and subjected to a tensile test in the Y direction, the elongation rate Ey in the Y direction under a stress of 0.1 MPa. The polymer composite according to [4], wherein the polymer composite satisfies the following (formula 2) or the following (formula 3).
2 <Ex / Ey (Equation 2)
2 <Ey / Ex (Equation 3)
[6] The elongation rate Ex of the polymer complex is 15% or more, or
The polymer complex according to [5], wherein the elongation rate Eye of the polymer complex is 15% or more.
[7] The polymer complex according to any one of [1] to [6], wherein the fiber constituting the fiber structure has a tensile strength of 1 GPa or more.
[8] The polymer composite according to any one of [1] to [7], wherein the fiber structure is a woven fabric, a knitted fabric, a non-woven fabric, or a woven fabric.
[9] A surface layer material using the polymer complex according to any one of [1] to [8].
[10] A robot provided with the surface layer material according to [9].
[11] A method for producing a polymer complex, which is a method for producing a polymer complex.
A host group-containing monomer, a guest group-containing monomer, and a fiber structure are prepared.
The host group-containing monomer and the guest group-containing monomer are polymerized to form a polymer.
A method for producing a polymer complex, which comprises compounding the polymer and the fiber structure.
[12] The production method according to [11], wherein the polymer complex is the polymer complex according to any one of [1] to [7].
[13] A polymer complex produced by the production method according to [11] or [12].

According to the polymer composite according to the present invention, lightness, flexibility, elasticity, durability, high strength (particularly cut resistance), and anisotropy (with respect to elasticity and strength) are additive. It is possible to propose a functional polymer structure that can be realized synergistically, and in particular, can realize elasticity in a certain direction. As a result, it is possible to propose materials that require high strength and flexibility. For example, like a nursing robot, the movable area has elasticity while having high strength and durability, and the human body. It is possible to propose a high-dimensional functional material such that the part in contact with the body has flexibility.

FIG. 1 is a schematic view showing an example of a polymer complex according to the present invention. FIG. 2 is a cross-sectional view showing a polymer complex according to the present invention used as a surface layer material for a joint portion of a robot.

[Definition]
"Polymer: polymer (compound)" is a structure composed of a molecule having a large molecular weight (for example, a molecular weight of 10,000 or more) and a unit obtained from a molecule having a small molecular weight substantially or conceptually by repeating it many times. means. Examples of the polymer include natural polymers and synthetic polymers, and the constituent substances may also be inorganic substances and / or organic substances. In the present invention, synthetic polymers, particularly organic synthetic polymers, such as resins, plastics and synthetic fibers, are preferred. The polymer may have various shapes such as linear and / or branched, star-shaped, comb-shaped, and brush-shaped. Further, the polymer may be a polymer, a copolymer (random, alternating, block, etc.), or a polypolymer.
"Anisotropy" means that the properties of a substance (eg, a polymer complex) do not depend on the distribution or direction (two-dimensional, three-dimensional) of the substance, for example, the substance according to the present invention. In the case of a polymer composite, physical properties (pull, shrinkage, shearing, bending, recovery, etc.) in each of the X direction, Y direction, and / or Z direction [horizontal direction, longitudinal (orthogonal) direction, thickness direction]. Means different.
"ISO 13997: 1999" is "Protective clothing-Mechanical properties-Determination of resistance to cutting by sharp objects (MOD)". -Mechanical properties-Cut resistance test method for sharp objects ".
"Tensile strength" can be measured by, for example, JIS K 7164 (ISO 527-4).
The "elongation rate" can be measured by, for example, the grab method described in the JIS L 1096 woven fabric and knitted fabric test method.
"Cyclodextrin (CD)" is a kind of cyclic oligosaccharide having a cyclic structure in which D-glucose is usually bound by 6 to 8 α-1,4 glycosidic bonds. Cyclodextrins are generally α-cyclodextrin (cyclohexaamylose; α-CD) with 6 bonds and β-cyclodextrin (cycloheptaamylose; β-CD) with 7 bonds. ), 8 bonds are called γ-cyclodextrin (cyclooctamylose; γ-CD).

[Polymer complex]
The polymer composite according to the present invention is composed of a polymer composed of a host group-containing monomer (monomer), a guest group-containing monomer (monomer), and a fiber structure. ..

(High molecular)
The polymer includes a host group-containing monomer (monomer) and a guest group-containing monomer (monomer). In the present invention, the polymer mainly functions as flexibility, elasticity, and durability (self-healing property) in the polymer complex.

In a polymer, a host group and a guest group derived from the above-mentioned monomer form a clathrate complex (clathrate compound) by a so-called host-guest interaction. Host-guest interactions can occur between molecules (or within supramolecular), which causes macromolecules to form crosslinked structures. The cross-linking points in the cross-linked structure are inclusion complexes based on host-guest interactions. The host-guest interaction is reversible, and the occurrence (and resulting binding) of the interaction between the host and guest groups and the elimination (and resulting dissociation) of this interaction occur reversibly. Therefore, in the present invention, the polymer can exhibit high breaking strain and is excellent in flexibility and elasticity. Moreover, since the host-guest interaction is reversible, the polymer becomes a material having high self-healing property.

<Monomer containing host group>
The host group may have a substituent or may include a derivative of the host group. Host groups include cyclodextrin, calixarene, crown ethers, cyclophane, cucurbituril, and derivatives thereof, which may have substituents, and one or more combinations thereof.

Specific examples of the host group include cyclodextrin (α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin), calix [6] allene sulfonic acid, calix [8] allene sulfonic acid, 12-crown-4,18. − Crown-6, [6] paracyclophane, [2,2] paracyclophane, kukurubit [6] uryl, kukurubit [8] uryl, etc., which is one or a combination of two or more. It is a cyclodextrin, more preferably α-cyclodextrin, β-cyclodextrin and / or γ-cyclodextrin.

The host group is preferably cyclodextrin or a derivative thereof. In this case, the host-guest interaction between the host group of the host polymer and the guest group of the guest polymer is likely to occur, the mechanical properties of the polymer material are improved, and in particular, the breaking strain is excellent, and the elongation rate and flexibility are excellent. It has excellent properties and can improve the transparency of polymer materials. The type of cyclodextrin derivative is not particularly limited, and various cyclodextrin derivatives can be used.

Examples of the host group-containing monomer include vinyl-based monomers containing one or more (preferably one) host groups. The types of host groups are as described above. Examples of the host group-containing monomer include a polymerizable monomer represented by the following formula (1).

In the formula (1), Q is O or NH, and NH is preferable. The CD is a cyclodextrin, preferably α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin. ^Ra is a hydrogen atom or a methyl group.

Examples of the monomer represented by the formula (1) include 6- (meth) acrylamide-α-cyclodextrin, 6- (meth) acrylamide-β-cyclodextrin, α-cyclodextrin methacrylate, β-cyclodextrin methacrylate, and α. One or a combination of two or more selected from -cyclodextrin acrylate, β-cyclodextrin acrylate, etc., or an isomer thereof, or a part or all of these substituted with a substituent. May be.

The host group-containing monomer can be produced by a known method (for example, the method disclosed in International Publication No. 2013/162019).

<Guest group-containing monomer>
Examples of the guest group include one or a combination of two or more selected from an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group and the like, which may have a substituent.

Specific examples of the alkyl group include linear, branched or cyclic C1-18 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Examples thereof include one or a combination of two or more selected from alkyl groups such as n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, isohexyl, dodecyl, octadecyl and adamantyl, preferably an adamantyl group or a butyl group. Particularly preferably, it is an adamantyl group.

The alkyl group is one or a combination of two or more selected from a substituent, for example, a halogen atom (for example, fluorine, chlorine, bromine, etc.), a carboxyl group, an ester group, an amide group, a hydroxyl group which may be protected, and the like. However, it is preferable to have about 1 to 3 of them. It may be an alkyl group to which ferrocene, which is an organometallic complex, is bonded as a substituent.

Specific examples of the aryl group include, for example, a monocyclic or two or more aryl groups, and one or a combination of two or more selected from phenyl, toluyl, xylyl, naphthyl, anthryl, and phenanthryl is preferable. It is a phenyl group. The aryl group is, for example, an alkyl group (for example, C1-18 alkyl group, etc.), a nitro group, a halogen atom (for example, fluorine, chlorine, bromine, etc.), a carboxyl group, an ester group, an amide group, an azo group having an aryl group. , One kind or a combination of two or more kinds selected from substituents such as hydroxyl groups which may be protected may be mentioned, and preferably about 1 to 3 may be possessed.

Specific examples of the arylalkyl group include a linear or branched lower alkyl having 1 to 3 carbon atoms in which the above-mentioned monocyclic or two or more aryl groups are substituted. Specifically, one or a combination of two or more selected from a benzyl group, a naphthylmethyl group, an anthracenemethyl group, a pyrenemethyl group and the like can be mentioned, and a benzyl group and a naphthylmethyl group are preferable.

Aryl groups are protected, for example, alkyl groups (eg, C1-18 alkyl groups, etc.), halogen atoms (eg, fluorine, chlorine, bromine, etc.), carboxyl groups, ester groups, amide groups, azo groups with aryl groups, etc. Examples thereof include one type or a combination of two or more types selected from substituents such as hydroxyl groups, and preferably having about 1 to 3 of these. For example, one or a combination of two or more selected from hydroxyphenylmethyl group, methylphenylmethyl group, dimethylphenylmethyl group, trimethylphenylmethyl group, carboxyphenylmethyl group, hydroxymethylphenylmethyl group, triphenylmethyl group and the like. Can be mentioned.

Examples of the guest group-containing monomer include vinyl-based monomers containing one or more (preferably one) guest groups. The types of guest groups are as described above. Examples of the guest group-containing monomer include a monomer represented by the following formula (2).

In the formula (2), A is an aryl group which may have a substituent, C (O) OR1 or C (O) NHR1, and R1 is an alkyl group which may have a substituent, a substituent. It is an aryl group which may have a group or an arylalkyl group which may have a substituent. R ^b is a hydrogen atom or a methyl group.

In the above formula (2), examples of the alkyl group of the alkyl group represented by R1 which may have a substituent include linear, branched or cyclic C1-18 alkyl groups. Specifically, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, isohexyl, dodecyl, octadecyl, and adamantyl. One or a combination of two or more selected from. Of these, an adamantyl group or a butyl group is preferable, and an adamantyl group is particularly preferable. Examples of the alkyl group include one or a combination of two or more selected from halogen atoms (for example, fluorine, chlorine, bromine, etc.), carboxyl groups, ester groups, amide groups, hydroxyl groups which may be protected, and the like. It is preferable to have about 1 to 3 of these. It may be an alkyl group to which ferrocene, which is an organometallic complex, is bonded as a substituent.

In the above formula (2), examples of the aryl group of the aryl group represented by A and R1 which may have a substituent include a monocyclic aryl group or an aryl group having two or more rings, and specifically, phenyl. , Truil, xylyl, naphthyl, anthrill, phenylthrill and the like, or a combination of two or more thereof. Of these, it is preferably a phenyl group. The aryl group is, for example, an alkyl group (for example, C1-18 alkyl group, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.), a carboxyl group, an ester group, an amide group, an azo group having an aryl group, and protection. Examples thereof include one type or a combination of two or more types selected from the hydroxyl groups which may be used, and preferably having about 1 to 3 of these.

In the above formula (2), the arylalkyl group of the arylalkyl group which may have a substituent, which is represented by R1, is, for example, a linear or branched lower alkyl having 1 to 3 carbon atoms. Examples thereof include groups substituted with the above-mentioned monocyclic or two or more aryl groups. Specifically, one or a combination of two or more selected from a benzyl group, a naphthylmethyl group, an anthracenemethyl group, a pyrenemethyl group and the like can be mentioned, and a benzyl group and a naphthylmethyl group are preferable. The aryl group is, for example, an alkyl group (for example, C1-18 alkyl group, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.), a carboxyl group, an ester group, an amide group, an azo group having an aryl group, and protection. Examples thereof include one type or a combination of two or more types selected from hydroxyl groups and the like, and preferably having about 1 to 3 of these. For example, one or a combination of two or more selected from hydroxyphenylmethyl group, methylphenylmethyl group, dimethylphenylmethyl group, trimethylphenylmethyl group, carboxyphenylmethyl group, hydroxymethylphenylmethyl group, triphenylmethyl group and the like. Can be mentioned.

The monomer represented by the formula (2) is preferably n-butyl acrylate, t-butyl acrylate, N- (1-adamantyl) acrylamide, 2-ethyl-2-adamantyl acrylate, and N-benzylacrylamide. , N-1-naphthylmethylacrylamide, one or a combination of two or more selected from styrene.

As the monomer represented by the formula (2), when A is an aryl group which may have a substituent, a commercially available monomer (styrene or the like) can be used as it is. The host group-containing monomer and guest group-containing monomer as described above can be produced by a known method (for example, the method disclosed in International Publication No. 2013/162019).

As the ionic polymerizable monomer, a salt of (meth) acrylic acid, a salt of styrene sulfonic acid, (meth) acrylamide having a quaternary ammonium salt in the side chain, and a (meth) having a quaternary ammonium salt in the side chain. Acrylic ester can be mentioned. Specific examples of the ionic polymerizable monomer include sodium (meth) acrylate, sodium styrene sulfonate, dimethylaminopropylacrylamide methyl quaternary salt, (3-acrylamidepropyl) trimethylammonium chloride and the like.

The guest group-containing monomer as described above can be produced by a known method (for example, the method disclosed in International Publication No. 2013/162019).

<monomer>
In the present invention, the basic monomer can specifically contain at least one of a (meth) acrylate monomer and a (meth) acrylate oligomer as a resin component. (Meta) acrylate means acrylate and methacrylate.

The (meth) acrylate monomer may be a mono (meth) acrylate, a poly (meth) acrylate, or a mixture thereof. Specific examples of the mono (meth) acrylate include isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and cyclohexyl. (Meta) acrylate, (meth) acrylic acid, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) ) Acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate , Decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, poly One or a mixture of two or more selected from the group consisting of oxyethylene nonylphenyl ether acrylate is exemplified. In the present invention, preferably one or two selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth) acrylate. The above mixture, more preferably ethyl (meth) acrylate, butyl (meth) acrylate or a mixture thereof.

Specific examples of the poly (meth) acrylate include butanediol di (meth) acrylate, hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, decanediol di (meth) acrylate, and 2-butyl-2-ethyl. -1,3-Propanediol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, triethylene glycol di (meth) Acrylate, tetraethylenene glycol di (meth) acrylate, tricyclodecanedimethylol di (meth) acrylate, 1,4-butane polyol di (meth) acrylate, 1,6-hexane polyol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, polyester di (meth) acrylate, tris ( 2-Hydoxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecanedimethylol di (meth) acrylate, EO adduct di (meth) acrylate of bisphenol A, Di (meth) acrylate of polyol of hydrogenated bisphenol A or PO adduct, epoxy (meth) acrylate with (meth) acrylate added to diglycidyl ether of bisphenol A, triethylene glycol divinyl ether, tri Methylolpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane EO adduct tri (meth) acrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetra (meth) acrylate, tetrafurfuryl alcohol oligo (meth) ) Acrylate, ethylcarbitol oligo (meth) acrylate, 1,4-butanediol oligo (meth) acrylate, 1,6-hexanediol oligo (meth) acrylate, trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) ) Acrylate, (Poly) Urethane (Meta) Acrylate, (Poly) butadiene (Meta) One or a mixture of two or more selected from the group consisting of acrylates is exemplified.

(Fiber structure)
In the present invention, the polymer complex comprises a fiber structure. The fiber structure mainly functions as high strength (particularly, cut resistance) and anisotropy (with respect to elasticity and high strength) in the polymer complex.

In the present invention, the fiber structure is a two-dimensional or three-dimensional structure constructed from one or more fibers, and has high strength (cut resistance) with respect to the polymer composite. Improving, in particular, imparting anisotropy to the polymer composite with respect to strength (cut resistance) and stretchability. The strength (cut resistance) can be improved by the composition of the fiber and the two-dimensional or three-dimensional structure in the fiber structure. In addition, the anisotropy related to strength and elasticity can be controlled particularly by a three-dimensional structure. When a knit is formed by using high-strength fibers (for example, polyamide fiber or the like) as the fiber structure, a fiber structure having anisotropy in the horizontal direction and the vertical direction of the knit can be obtained. By controlling the composition of the knitted fabric, it is possible to control the anisotropy of strength (cut resistance) and elasticity.

<fiber>
The fibers may be natural or synthetic as long as they are capable of constructing flexibility, strength and elasticity, but (chemical) synthetic fibers are preferably used. Examples of the fiber include refined fiber, regenerated fiber, semi-synthetic fiber, synthetic fiber, inorganic fiber, synthetic fiber made of inorganic substance and organic substance, and the like.

Examples of "refined fibers (natural polymers)" include cellulosic fibers (lyocell, tencel). "Regenerated fiber (natural polymer)" includes cellulose-based fiber (rayon, biscous rayon, polynosic, cupra, cuprammonium rayon), protein-based fiber (casein fiber, peanut protein fiber, corn protein fiber, soybean protein fiber, etc. (Recycled silk thread), other fibers (argin fiber, chitin fiber, mannan fiber, rubber fiber) and the like are exemplified. Examples of the "semi-synthetic fiber (semi-synthetic polymer)" include cellulosic fibers (acetate, triacetate, oxide acetate), protein fibers (promix), natural rubber fibers (rubber chloride, rubber hydrochloride) and the like. .. "Synthetic fibers (synthetic polymers)" include polyamide fibers (nylon, nylon 6, nylon 66, aromatic nylon), aromatic polyamide fibers (aramid), polyvinyl alcohol (viniron), and polyvinylidene chloride (polyvinylidene chloride). Vinylidene), polyvinyl chloride fiber (polyvinyl chloride), polyester fiber (polyester), polyacrylonitrile fiber (polyacrylonitrile fiber, modacryl fiber), polyolefin fiber (polyethylene fiber, polypropylene fiber, polystyrene fiber), poly Examples thereof include ether ester fibers (lexe, success), polyurethane fibers (polyurethane), polyimide fibers (polykido), acrylate fibers, ethylene vinyl alcohol fibers, polyclaric fibers and the like. Examples of the "carbon fiber" are fibers made by carbonizing acrylic fiber or pitch (a by-product of petroleum, coal, coal tar, etc.) at a high temperature, and examples thereof include PAN-based carbon fiber and pitch-based carbon fiber. .. Further, glass fiber (non-alkali glass fiber such as quartz glass) and artificial mineral fiber (rock wool, glass wool, ceramic fiber) can be used.

In the present invention, preferably, aramid fiber, polyarylate fiber, glass fiber, (ultra high molecular weight) polyethylene fiber, PBO (polyparaphenylene benzoxazole) fiber, carbon fiber and the like are preferably used.

The fibers may be filaments (long fibers: multifilaments, single fibers: monofilaments), staples (short fibers). Further, after spinning, stretching (a treatment of stretching to impart appropriate strength and elongation to the fiber) may be performed. Further, as the work of twisting, drawing, etc., a drawn yarn (FOY), a semi-drawn yarn (POY), and a drawn processed yarn (DTY) may be performed. Furthermore, after spinning, spinning (spinning staples into yarn), blended spinning (spinning by mixing two or more different staples), twisting (twisting filament yarn and spun yarn), interlacing. Twisting (twisting while mixing two or more different types of yarn) or the like can be performed to obtain a desired fiber form (yarn). Further, the cross section of the fiber can also have various shapes such as a circular shape, an elliptical shape, a polygonal shape, a Y shape, and a star shape, and can be configured as a hollow fiber having a hollow inside the fiber.

In the present invention, the fibers constituting the fiber structure can be preferably used as long as the tensile strength is 1 GPa or more.

The fiber can be formed as a "woven fabric", a "knitted fabric", a "woven fabric", a "nonwoven fabric" or a mixture thereof (fabric or fabric form) after being spun or threaded to form a fiber structure.

(anisotropy)
In the present invention, the incision force and the elongation rate of the polymer composite are different in the horizontal direction (X direction) of the polymer composite and in the direction perpendicular to the X direction (Y direction). It is characterized by having an anisotropy. In the present invention, "anisotropic" can be expressed as the elongation ratio and the ratio of the incision force between the X direction and the Y direction (X / Y) or the ratio between the Y direction and the X direction (Y / X). Is.

In the present invention, due to the above anisotropy, it is suitably used for surface material applications in places where it expands and contracts in a certain direction, especially for robot surface material applications. By having anisotropy of elongation rate, it is possible to install it in a stretchable place such as a driving part of a robot, and by having anisotropy of cut force, it is possible to provide a surface layer material having a high protective function. Is possible.

(Formula (1) and formula (2) or formula (3))
In the present invention, it is preferable that the following mathematical formula (1) and mathematical formula (2) or mathematical formula (3) are satisfied. For example, when the polymer composite according to the present invention has a three-dimensional structure as shown in FIG. 1, it has a horizontal direction (X direction), a direction perpendicular to the X direction (Y direction), and a thickness. A numerical value can be measured and calculated as a direction (Z direction).

(Cut force ratio: Sx / Sy)
In the polymer composite of the present invention, the incision force Sx in the horizontal direction (X direction) of the polymer composite and the incision force Sy in the direction perpendicular to the X direction (Y direction) are as follows (Equation 1). ) Is satisfied.
2 <Sx / Sy (Equation 1)

In the present invention, Sx / Sy is 2 or more, preferably 3 or more, and more preferably 5 or more. A member that requires flexibility, elasticity, durability, strength, and protection by having Sx / Sy having the above numerical value, that is, having a high cutting force in the X direction, for example, a robot. It is possible to provide a surface layer material having a high protection function in a specific direction in a part that is easily damaged such as a scratch such as a driving part of the robot.

Sx and Sy are values measured by a measuring method based on ISO 13997 (JIS T 8052). In this measurement method, the test blade is slowly moved while gradually applying a load to the test blade in contact with the sample, and the cut resistance (cutting force) is determined from the force when the blade penetrates the sample. ) Is a method of evaluation. Penetration of the sample is detected by electrical contact between the blade and the sample holder located below the sample. Specifically, the cutting load (N) required when the test piece is cut by moving the test cutting tool by 20 mm at a speed of 150 mm / min on the test piece attached to the test device can be measured.

(Growth ratio: Ex / Ey)
The polymer composite in the present invention has a stress of 0 when the polymer composite is cut into 50 mm along the X direction, 10 mm in the Y direction, and 1 mm in thickness and subjected to a tensile test in the X direction. The elongation rate Ex in the X direction at 1 MPa, and
When the polymer complex was cut out to 50 mm along the Y direction, 10 mm in the X direction, and 1 mm in thickness and subjected to a tensile test in the Y direction, the elongation rate Ey in the Y direction under a stress of 0.1 MPa. Satisfies the following (Equation 2) or (Equation 3).
2 <Ex / Ey (Equation 2)
2 <Ey / Ex (Equation 3)

In the present invention, Ex / Ey is 2 or more, preferably 3 or more, and more preferably 4 or more. Since Ex / Ey has the above numerical value, that is, it has high elasticity in the X direction, a member that requires flexibility, elasticity, durability, strength, and protection, for example, a robot. By aligning the expansion and contraction direction of the drive unit with the direction of the elastomer having higher elasticity (Y direction) and installing it at a place where the drive unit expands and contracts, the higher the value of Ex / Ey, the more the drive unit becomes. It can be driven without resistance.

In the present invention, Ey / Ex is 2 excesses, preferably 3 excesses, and more preferably 4 excesses. Since Ey / Ex has the above numerical value, that is, it has high elasticity in the Y direction, a member that requires flexibility, elasticity, durability, strength, and protection, for example, a robot. By aligning the expansion and contraction direction of the drive unit with the direction of the elastomer having higher elasticity (Y direction) and installing it at a place where the drive unit expands and contracts, the higher the value of Ey / Ex, the more the drive unit becomes. It can be driven without resistance.

Further, when the polymer composite has Ex / Ey or Ey / Ex satisfying the above numerical values and the incision force ratio (Sx / Sy) satisfies the above numerical values, the elongation rate is particularly high. Since the directions in which the cutting force is high are orthogonal to each other, it can be more preferably used as a surface layer material to be installed in a stretchable place such as a driving part of a robot.

According to a preferred embodiment of the present invention, the elongation rate Ex of the polymer complex is preferably 15% or more, preferably 30% or more, and more preferably 60% or more. Further, the elongation rate Ey of the polymer complex is preferably 15% or more, preferably 30 or more, and more preferably 60% or more.

When Ex or Ey is 15% or more, it can be applied to members requiring flexibility, elasticity, durability, strength, and protection, for example, many movable members, and the elongation rate Ex or If Ey is 30% or more, it can be applied to, for example, knee members and elbow members that require the highest elongation rate of humanoid robots. Further, if the elongation rate Ex or Ey is 60% or more, it can be used for a drive member other than a humanoid robot that requires a higher elongation rate, and the required elongation rate is low. However, it is preferable because it can be stretched with a smaller force.

Ex and Ey are values measured by a measuring method based on JIS L 1096. In this measuring method, a sample is cut out to 100 mm in the X direction, 10 mm in the Y direction, and 1 mm in thickness, and a tensile test is performed in the X direction. The stress was calculated by dividing the measured load (N) by the cross-sectional area of the sample, and the elongation rate at 0.1 MPa was measured. Further, Ey cuts a sample into 100 mm along the Y direction, 10 mm in the X direction, and 1 mm in thickness, and performs a tensile test in the X direction. The stress can be calculated by dividing the measured load (N) by the cross-sectional area of the sample, and the elongation rate at 0.1 MPa can be measured.

[Manufacturing method of polymer complex]
In one aspect of the present invention, a method for producing a polymer complex can be proposed, and the method for producing the polymer complex is described.
A host group-containing monomer, a guest group-containing monomer, and a fiber structure are prepared.
The host group-containing monomer and the guest group-containing monomer are polymerized to form a polymer.
It includes compounding the polymer and the fiber structure.
The contents, materials, preparation, etc. of the polymer and the fiber structure may be the same as those described in the section of [Polymer complex].

(polymerization)
As a polymerization method, a polymerization method such as radical polymerization, cationic polymerization, anion polymerization, coordination polymerization, or polycondensation of the host group-containing monomer and the guest group-containing monomer can be used, and radical polymerization is preferably used. be able to. In the polymerization, a polymerization initiator, a stabilizer, an accelerator, a solvent, an ionic substance, heating, UV rays, or the like can be used.

As the polymerization initiator used for radical polymerization, a dihalogen, an azo compound, an organic peroxide, a redox initiator in which an oxidizing agent and a reducing agent are combined, and the like can be used. A solvent may be used for radical polymerization. The polymerization reaction is started by mixing a monomer with a polymerization initiator, and in some cases a solvent, and generating radicals from the polymerization initiator by heating, UV light irradiation, or the like, depending on the type of the polymerization initiator. After the polymerization is completed, purification treatment or the like can be performed as necessary to obtain the desired polymer.

(Composite)
In the present invention, the polymer and the fiber structure are composited. The composite polymer complex should exhibit light weight, flexibility, elasticity, and high strength (particularly cut resistance), as well as durability and anisotropy (with respect to elasticity and strength). Can be done. According to a preferred embodiment of the present invention, it is preferable to appropriately prepare the interaction between the polymer and the fiber structure in order to fully exert all the above-mentioned functions.

In the present invention, the composite of the polymer and the fiber structure means that the host group-containing monomer and the guest group-containing monomer are polymerized in the fiber structure (in the presence of the fiber structure). Proposed. For example, the host group-containing monomer and the guest group-containing monomer are mixed with the fiber structure and then polymerized, or the host group-containing monomer and the guest group-containing monomer are added to the fiber structure. After that, it may be polymerized. Alternatively, the monomer constituting the polymer may be polymerized only with the host group-containing monomer and the guest group-containing monomer. In this case, the obtained polymer is applied to the fiber structure to form a composite.

As a method of compounding, a method of adhering the polymer and the fiber structure and then performing heat pressing to form the composite can be used.

The contents, materials, preparation, etc. of the polymer and the fiber structure may be the same as those described in the section of [Polymer complex].

In the present invention, the polymer composite produced by the above method for producing a polymer composite can also be proposed in one aspect of the present invention.

[Use]
The polymer complex according to the present invention is used as a functional material. Therefore, for example, it can be used as a surface material of a product. Particularly preferably, it can be used as a surface layer material (exterior material) of a robot. Therefore, in the present invention, it is possible to propose a robot provided with a surface layer material formed of the polymer complex according to the present invention. In fact, as shown in FIG. 2, it is used as a surface layer material in the joint portion of the robot. In particular, since the (nursing care) robot comes into direct contact with the person to be cared for, the surface layer material is required to be flexible, and the function (strength) and durability to protect the inside of the robot are required. In the driving unit (movable area) of the robot, it is necessary to have elasticity (flexibility) and flexibility (particularly, in a certain direction). Therefore, the polymer complex according to the present invention is preferably used as a surface layer material for a (care) robot that satisfies the need.

The contents of the present invention will be described with reference to the following examples, but the scope of the present invention is not construed as being limited to these examples. In addition, various aspects of the present invention disclosed in the present specification allow those skilled in the art to easily carry out the present invention from the present examples.

[Preparation of fibers]
(1) Polyarylate fiber knitting 22tex XXION fiber (manufactured by KB Seiren Co., Ltd.) is prepared and warp-knitted using this to obtain a polyarylate fiber knitting having ^{a thickness of 1.03 mm and a basis weight of 61.18 g / m 2.} It was.
(2) Glass fiber knitting A 67.5 tex glass fiber (manufactured by Central Glass Fiber Co., Ltd.) was prepared and warped using this to obtain a glass fiber knitted fabric having ^{a thickness of 0.7 mm and a grain size of 370 g / m 2.} ..

[Preparation of host group-containing monomer]
Β-Cyclodextrin (19.4 parts, Yushiro Chemical Industry Co., Ltd.), acetic anhydride (100.0 parts, Tokyo Kasei) and pyridine (129.2 parts, Tokyo Kasei) were added to the eggplant flask, and the mixture was stirred at 70 ° C. for 4 hours. , Reacted. Then, methanol (31.4 parts, Kishida Chemistry) was added under ice-cooling, and the mixture was stirred for 20 minutes to obtain a reaction solution. The reaction solution was added dropwise to water to precipitate TAcβ-cyclodextrin, and a precipitate was obtained by centrifugation (3500 rpm, 3 minutes). The precipitate was suction filtered and dried overnight to separate the precipitate. The precipitate was vacuum dried for 3 days to obtain acetylated β-cyclodextrin (CD monomer) as a host group-containing monomer.

[Example 1]
(Preparation of polymer precursor solution)
Ethyl acrylate (EA, 100.0 parts, Nakaraitesk Co., Ltd.), CD monomer (12.1 parts) as main chain monomer, 2-ethyl-2-adamantyl acrylate (2.4 parts, 2.4 parts) as guest monomer in eggplant flask Osaka Organic Chemical Industry Co., Ltd.) was added and treated in an ultrasonic cleaning tank for 60 minutes to completely dissolve the CD monomer, and then Acrylic 184 (0.4 part, BASF) was added as a photopolymerization initiator to dissolve it. A molecular precursor solution was obtained.
(Preparation of polymer complex)
A jig for film formation was formed by sandwiching a 1.0 mm spacer between two glass plates. In the meantime, after setting the polyarylate fiber knitted fabric, the polymer precursor solution is put in, UV light (170 mW / cm ² ) is irradiated from the glass surface for 60 minutes, and the obtained sample is taken out and heated at 80 ° C. The polymer composite 1 was obtained by performing vacuum drying by heating in the evening.
[Example 2]
In Example 1, a polymer complex 2 was obtained in the same manner except that ethyl acrylate (EA) was changed to butyl acrylate (BA, 128.0 parts, Nacalai Tesque).
[Example 3]
In Example 1, the polymer complex 3 was obtained in the same manner except that the polyarylate fiber knit was changed to a glass fiber knit.
[Example 4]
In Example 1, the polymer composite 4 was obtained in the same manner except that ethyl acrylate (EA) was changed to the above butyl acrylate (BA) and polyarylate fiber knitting was changed to glass fiber knitting.

[Comparative Example 1]
In Example 1, the polymer 1 was obtained in the same manner except that the polyarylate fiber knit was not used.
[Comparative Example 2]
In Example 1, the ethyl acrylate (EA) was changed to the above-mentioned butyl acrylate (BA), and the polymer 2 was obtained in the same manner except that the polyarylate fiber knitting was not used.

〔Evaluation test〕
The following evaluations were made on the polymer complex of Examples and the polymer of Comparative Examples.

[Tensile test evaluation]
Ex and Ey were measured by a measuring method based on JIS L 1096.
For Ex, a sample is cut out to 50 mm in the X direction, 10 mm in the Y direction, and 1 mm in thickness, and a tensile test is performed in the X direction. The stress was calculated by dividing the measured load (N) by the cross-sectional area of the sample, and the elongation rate at 0.1 MPa was measured.
For Ey, a sample is cut out to 50 mm in the Y direction, 10 mm in the X direction, and 1 mm in thickness, and a tensile test is performed in the X direction. The stress was calculated by dividing the measured load (N) by the cross-sectional area of the sample, and the elongation rate at 0.1 MPa was measured.
These measurement results are as shown in Table 1 below.

[Incision strength evaluation test]
Sx and Sy were measured by a measuring method compliant with ISO 13997 (JIS T 8052).
In this measurement method, the test blade is slowly moved while gradually applying a load to the test blade in contact with the sample, and the cut resistance (cutting force) is determined from the force when the blade penetrates the sample. ) Is a method of evaluation. Penetration of the sample is detected by electrical contact between the blade and the sample holder located below the sample. Specifically, the cutting load (N) required for cutting the test piece was measured by moving the test cutting tool by 2 mm at a speed of 150 mm / min on the test piece attached to the test device.
These measurement results are as shown in Table 1 below.

〔Evaluation results〕
As shown in Table 1 below, the present invention (Example) is compared with Comparative Example.
It was found that the incision force ratio (Sx / Sy) and the elongation ratio (Ex / Ey) were high. From these results, it is clearly understood that it exerts an excellent effect in the protective function and elasticity in a specific direction.

The polymer composite of the present invention has the functions of high strength, flexibility, and elasticity, and has high elasticity in a certain direction, so that it can come into direct and flexible contact with the human body. It is possible to realize flexibility and elasticity so that a movable region can be freely realized, and it is suitable as a material having strength to protect an internal structure (for example, a surface layer material for a robot).

Claims (12)

It is a polymer complex
It is equipped with a polymer and a fiber structure.
A polymer complex in which the polymer is composed of a host group-containing monomer and a guest group-containing monomer. The host group is a cyclodextrin, calixarene, crown ether, cyclophane, cucurbituril, and derivatives thereof, which may have a substituent, and one or a combination of two or more thereof.
The guest group is one or a combination of two or more selected from alkyl groups, cycloalkyl groups, aryl groups, and arylalkyl groups, which may have substituents;
The polymer composite according to claim 1, wherein the monomer in the host group-containing monomer or the monomer in the guest group-containing monomer is a vinyl-based monomer. The host group-containing monomer is a polymerizable monomer represented by the following formula (1), or
The polymer complex according to claim 1, wherein the guest group-containing monomer is a polymerizable monomer represented by the following formula (2).

[In the above formula (1),
Q is O or NH,
CD is cyclodextrin,
^Ra is a hydrogen atom or a methyl group. ]

[In the above equation (2),
A is an aryl group which may have a substituent, C (O) OR1 or C (O) NHR1.
R1 is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an arylalkyl group which may have a substituent.
R ^b is a hydrogen atom or a methyl group. ] Each of the cutting force and the elongation rate of the polymer composite has anisotropy in the horizontal direction (X direction) of the polymer composite and in the direction perpendicular to the X direction (Y direction). The polymer composite according to any one of claims 1 to 3. The incision force Sx in the X direction and the incision force Sy in the Y direction satisfy the following (Equation 1).
2 <Sx / Sy (Equation 1)
[In Equation 1, Sx and Sy are values measured by a measuring method based on ISO 13997 (JIS T 8052)].
When the polymer complex was cut out to 50 mm along the X direction, 10 mm in the Y direction, and 1 mm in thickness and subjected to a tensile test in the X direction, the elongation rate Ex in the X direction at a stress of 0.1 MPa. And then
When the polymer composite was cut out to 50 mm along the Y direction, 10 mm in the X direction, and 1 mm in thickness and subjected to a tensile test in the Y direction, the elongation rate Ey in the Y direction under a stress of 0.1 MPa. The polymer composite according to claim 4, wherein the polymer composite satisfies the following (formula 2) or the following (formula 3).
2 <Ex / Ey (Equation 2)
2 <Ey / Ex (Equation 3) The elongation rate Ex of the polymer complex is 15% or more, or
The polymer complex according to claim 5, wherein the elongation rate Eye of the polymer complex is 15% or more. The polymer complex according to any one of claims 1 to 6, wherein the fiber constituting the fiber structure has a tensile strength of 1 GPa or more. The polymer composite according to any one of claims 1 to 7, wherein the fiber structure is a woven fabric, a knitted fabric, a non-woven fabric, or a woven fabric. A surface layer material using the polymer complex according to any one of claims 1 to 8. A robot provided with the surface layer material according to claim 9. A method for producing a polymer complex,
A host group-containing monomer, a guest group-containing monomer, and a fiber structure are prepared.
The host group-containing monomer and the guest group-containing monomer are polymerized to form a polymer.
A method for producing a polymer complex, which comprises compounding the polymer and the fiber structure. The production method according to claim 11, wherein the polymer complex is the polymer complex according to any one of claims 1 to 7.

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