JP6507928B2 - Fibrous molded body, and composition for forming fiber - Google Patents

Description

  The present invention relates to a fibrous molded body and a composition for forming a fiber.

  Molded articles made of resin and metal may cause deformation such as elongation and breakage due to external force. Deformation of these compacts generally includes plastic deformation and often involves microscopic fracture. Therefore, after deformation, it is difficult to restore the molded body to its original state.

  On the other hand, metals, resins, ceramics and the like are known as shape memory materials. Shape memory materials exhibit shape recovery properties based on changes in crystal structure and phase transformations due to changes in molecular motion morphology. The shape memory material is excellent not only in shape recovery characteristics but also in vibration damping characteristics and the like. So far, metals and resins have been mainly considered as shape memory materials.

  The shape memory resin is a resin that recovers its original shape when the molded body is heated to a temperature above a certain temperature even if it is deformed by force. Main shape memory resins include polynorbornene, trans isoprene, styrene-butadiene copolymer, and polyurethane. For example, Patent Document 1 describes a norbornene resin, Patent Document 2 describes a trans-isoprene resin, Patent Document 3 describes a polyurethane resin, and Patent Document 4 describes a shape memory resin related to an acrylic resin.

Tokuhei 5-72405 Japanese Patent Application Publication No. 2004-250182 Japanese Patent Application Publication No. 2004-300368 Japanese Patent Application Laid-Open No. 7-292040

  The present invention provides a novel fibrous molded body which can have properties such as shape memory and a composition for obtaining the same.

で表され、Ｘ、Ｒ^１及びＲ^２がそれぞれ独立に２価の有機基で、Ｒ^３及びＲ^４がそれぞれ独立に水素原子又はメチル基である、ラジカル重合性化合物、及び単官能ラジカル重合性モノマーを、モノマー単位として含む第一の重合体と、直鎖状又は分岐状の第二の重合体と、を含有する、繊維状成形体に関する。 One aspect of the invention relates to compounds of formula (I):

A radically polymerizable compound in which X, R ¹ and R ² are each independently a divalent organic group, and R ³ and R ⁴ are each independently a hydrogen atom or a methyl group, and a monofunctional radically polymerizable The present invention relates to a fibrous formed body containing a first polymer containing a monomer as a monomer unit and a linear or branched second polymer.

  Another aspect of the present invention is a radically polymerizable compound represented by the formula (I), and a reactive monomer containing a monofunctional radically polymerizable monomer, and a linear or branched second polymer The present invention relates to a composition for forming a fiber, which is contained.

  Yet another aspect of the present invention relates to a method of producing a fibrous compact, comprising a first polymer and a linear or branched second polymer. In this method, the above-described composition for forming a fiber is introduced into a long flow path, and the first polymer is obtained by photoradical polymerization or thermal radical polymerization of a reactive monomer in the composition for forming a fiber in the flow path. Providing the step of generating Alternatively, this method comprises the steps of: forming a first polymer by photoradical polymerization or thermal radical polymerization of a reactive monomer in the above-mentioned composition for forming a fiber to obtain a resin molded product; And the step of cutting out the molded body.

  The fibrous molded body according to the disclosed several forms is strong and excellent in stress relaxation properties. In addition, the fibrous molded body disclosed can have the property of recovering shape upon heating when deformed by external force.

  The disclosed fibrous compact is superior to fibers of shape memory alloy in that it has a high rate of shape change, is light, is easy to process, can be colored, and the like. The fibrous molded body according to the disclosed several forms can be stretched to several times its original length with a small force because it is soft at high temperature and easily deformed like a rubber, and after cooling, it can be expanded. The deformed shape can be maintained. The deformed fibrous molded body can be restored to its original shape by heating under no load. Thus, the fibrous shaped body can also be used as a material for energy absorption and storage at high temperatures.

It is a schematic diagram which shows one Embodiment of the method of manufacturing a fibrous molded object by radical photopolymerization. It is a schematic diagram which shows one Embodiment of the method of manufacturing a fibrous molded object by thermal radical polymerization.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

で表されるラジカル重合性化合物、及び単官能ラジカル重合性モノマーを含む反応性モノマーと、第二の重合体とを含有する繊維形成用組成物から形成される。式（Ｉ）中、Ｘ、Ｒ^１及びＲ^２がそれぞれ独立に２価の有機基で、Ｒ^３及びＲ^４がそれぞれ独立に水素原子又はメチル基である。繊維形成用組成物中で反応性モノマーが重合することで、それら反応性モノマーに由来するモノマー単位から構成される第一の重合体が生成する。これにより、繊維形成用組成物が硬化して、繊維状成形体としての樹脂成形体（硬化体）を形成する。第一の重合体は、通常、第二の重合体と共有結合によって結合することなく、第二の重合体とは別の重合体として成形体中に形成される。 The fibrous shaped body according to one embodiment has the formula (I):

It is formed from the composition for fiber formation containing the reactive monomer containing the radically polymerizable compound represented by these, and a monofunctional radically polymerizable monomer, and a 2nd polymer. In formula (I), X, R ¹ and R ² each independently represent a divalent organic group, and R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. The reactive monomer is polymerized in the fiber-forming composition to form a first polymer composed of monomer units derived from the reactive monomer. Thereby, the composition for fiber formation hardens | cures and forms the resin molding (hardened body) as a fibrous molded object. The first polymer is generally formed in the molded product as a polymer separate from the second polymer without being covalently bonded to the second polymer.

  The fibrous molded body may be a resin molded body having an elongated shape, and the shape and size of the cross section thereof are not particularly limited. The cross section of the fibrous shaped body may be, for example, circular, oval, rectangular or amorphous. The fibrous shaped body may be a strip-like elongated body. A plurality of single yarns, which are fibrous shaped articles, may be twisted together. The maximum width of the cross section in the direction perpendicular to the longitudinal direction may be, for example, 1 μm to 10 mm for one fibrous molded body. The length of the fibrous formed body may be, for example, 10 times or more, 100 times or more, or 1000 times or less of the maximum width of the cross section of the fibrous formed body.

  The first polymer may contain cyclic monomer units represented by the following formula (II) derived from the compound of the formula (I). It is thought that the cyclic | annular monomer unit of Formula (II) contributes to expression of specific characteristics, such as shape memory property of a fibrous molded object. However, the first polymer may not necessarily contain the monomer unit of the formula (II).

で表される基であってもよい。式（１０）中、Ｙは置換基を有していてもよい環状基で、Ｚ^１及びＺ^２はそれぞれ独立に炭素原子、酸素原子、窒素原子、及び硫黄原子から選ばれる原子を含む官能基で、ｉ及びｊはそれぞれ独立に０〜２の整数である。＊は結合手を表す（これは他の式でも同様である）。Ｘが式（１０）の基であると、式（ＩＩ）の環状のモノマー単位が特に形成され易いと考えられる。環状基Ｙに対するＺ^１及びＺ^２の配置が、シス位であってもよいし、トランス位であってもよい。Ｚ^１及びＺ^２は、−Ｏ−、−ＯＣ（＝Ｏ）−、−Ｓ−、−ＳＣ（＝Ｏ）−、−ＯＣ（＝Ｓ）−、−ＮＲ^１０−（Ｒ^１０は水素原子又はアルキル基）、又は−ＯＮＨ−で表される基であってもよい。 X in the formulas (I) and (II) is, for example, the following formula (10):

It may be a group represented by In formula (10), Y is a cyclic group which may have a substituent, and Z ¹ and Z ² are each independently a functional group containing an atom selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom And i and j are each independently an integer of 0-2. * Represents a bond (this also applies to other formulas). When X is a group of the formula (10), it is considered that the cyclic monomer unit of the formula (II) is particularly easily formed. The arrangement of Z ¹ and Z ^{2 with} respect to the cyclic group Y may be cis or trans. Z ¹ and Z ² are —O—, —OC (= O) —, —S—, —SC (= O) —, —OC (= S) —, —NR ¹⁰ — (R ¹⁰ is a hydrogen atom or It may be an alkyl group) or a group represented by -ONH-.

  Y may be a cyclic group having 2 to 10 carbon atoms, and may contain a hetero atom selected from an oxygen atom, a nitrogen atom and a sulfur atom. The cyclic group Y is, for example, an alicyclic group, cyclic ether group, cyclic amine group, cyclic thioether group, cyclic ester group, cyclic amide group, cyclic thioester group, aromatic hydrocarbon group, heteroaromatic hydrocarbon group, or It may be a combination of these. The cyclic ether group may be a cyclic group that a monosaccharide or polysaccharide has. Although it does not specifically limit as a specific example of Y, The cyclic group represented by following formula (11), (12), (13), (14) or (15) is mentioned. From the viewpoint of the stress relaxation property of the fibrous molded body, Y may be a group of formula (11) (in particular, a 1,2-cyclohexanediyl group).

R ¹ and R ² in the formulas (I) and (II) may be the same as or different from each other, and may be a group represented by the following formula (20).

In formula (20), R ⁶ is a hydrocarbon group having 1 to 8 carbon atoms (such as an alkylene group), and is bonded to the nitrogen atom in formula (I) or (II). Z ³ is -O-, or ^{-NR 10} - ^(R 10 is a hydrogen atom or an alkyl group) is a group represented by. When R ¹ and R ² are a group of the formula (20), it is considered that a cyclic monomer unit of the formula (II) is particularly easily formed. The carbon number of R ⁶ may be two or more, or six or less, or four or less.

One specific example of the radically polymerizable compound of the formula (I) is a compound represented by the following formula (Ia). Here, Y, Z ¹ , Z ² , i and j are defined in the same manner as equation (10).

  Examples of the compound of the formula (Ia) include the following formulas (I-1), (I-2), (I-3), (I-4), (I-5), (I-5), (I-6) and (I-6) The compound represented by I-7) or (I-8) is mentioned.

  The compounds exemplified above can be used alone or in combination of two or more.

  The proportion of the radically polymerizable compound of the formula (I) in the composition for forming a fiber is 0.01 mol% or more, 0.1 mol% or more, or 0.5 mol% or more based on the total amount of reactive monomers. 10 mol% or less, 5 mol% or less, or 1 mol% or less. When the ratio of the radically polymerizable compound of the formula (I) is in these ranges, a further advantageous effect is obtained in that a cured product having excellent mechanical properties such as elongation and strength can be obtained.

  The compounds of formula (I) can be synthesized by conventional synthetic methods using commonly available raw materials as starting materials, as will be appreciated by those skilled in the art. For example, the compound of the formula (I) can be synthesized by the reaction of a cyclic diol compound or a cyclic diamine compound and a compound having a (meth) acryloyl group and an isocyanate group.

  The reactive monomer in the composition for fiber formation may contain alkyl (meth) acrylate and / or acrylonitrile as a monofunctional radically polymerizable monomer.

  The alkyl (meth) acrylate is an alkyl (meth) acrylate having an alkyl group having 1 to 16 carbon atoms which may have a substituent ((meth) acrylic acid and 1 carbon atom which may have a substituent) And esters with -16 alkyl alcohols). The substituent which the alkyl (meth) acrylate which has a C1-C16 alkyl group may have may contain an oxygen atom and / or a nitrogen atom.

  When the reactive monomer contains an alkyl (meth) acrylate having an alkyl group having 1 to 16 carbon atoms, the effect of being able to control the elastic modulus and the glass transition temperature (Tg) of the molded article is obtained.

  The proportion of the alkyl (meth) acrylate having 1 to 16 carbon atoms which may have a substituent in the composition for forming a fiber is 10% by mole or more and 15% by mole or more based on the total amount of reactive monomers Alternatively, it may be 20 mol% or more, and may be 95 mol% or less, 90 mol% or less, or 85 mol% or less. If the proportion of the alkyl (meth) acrylate having 1 to 16 carbon atoms which may have a substituent is within these ranges, it is possible to obtain a fibrous molded article having excellent mechanical properties such as elongation and strength. Further advantageous effects can be obtained.

  By using the alkyl (meth) acrylate having an alkyl group with a small number of carbon atoms, the elastic modulus of the cured fibrous molded body tends to be high, and the shape memory tends to be easily expressed. From such a viewpoint, the reactive monomer may contain, as a monofunctional radically polymerizable monomer, an alkyl (meth) acrylate having an alkyl group having 10 or less carbon atoms which may have a substituent. The proportion of the alkyl (meth) acrylate having a carbon number of 10 or less which may have a substituent in the composition for fiber formation is 8 mol% or more and 10 mol% or more based on the total amount of reactive monomers, Alternatively, it may be 15 mol% or more, or 55 mol% or less, 45 mol% or less, or 25 mol% or less. When the ratio of the alkyl (meth) acrylate having an alkyl group having 10 or less carbon atoms which may have a substituent is within these ranges, a fibrous molded article having a somewhat high elastic modulus and having shape memory property Further advantageous effects can be obtained in that it is easily formed. From the same viewpoint, the reactive monomer may contain a (meth) acrylate having an alkyl group having 8 or less carbon atoms which may have a substituent, and the ratio may be in the above numerical range. .

  Examples of the optionally substituted alkyl (meth) acrylate having 1 to 16 carbon atoms include ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, hexyl acrylate, Hexyl methacrylate, 2-ethylhexyl acrylate (EHA), 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-1-methylethyl methacrylate, 2-methoxyethyl acrylate (MEA), and N, N-dimethylaminoethyl acrylate is mentioned. The alkyl (meth) acrylate may be a compound having a glycidyl group, such as glycidyl methacrylate. These can be used alone or in combination of two or more.

  When the reactive monomer contains acrylonitrile, it tends to be likely to form a fibrous shaped article having a somewhat high elastic modulus and having shape memory. The combination of acrylonitrile and a (meth) acrylate having an alkyl group of 1 to 16 (or 1 to 10) carbon atoms is particularly advantageous in order to obtain a fibrous article having a high elastic modulus. The proportion of acrylonitrile in the fiber-forming composition may be 40 mol% or more, 50 mol% or more, or 70 mol% or more, 90 mol% or less, 85 mol%, based on the total amount of reactive monomers. % Or less, or 80 mol% or less. When the proportion of acrylonitrile is within these ranges, a further advantageous effect is obtained in that shape recovery is fast.

  The reactive monomer may contain, as a monofunctional radically polymerizable monomer, one or more compounds selected from vinyl ether, styrene and a styrene derivative. Examples of vinyl ethers include vinyl butyl ether, vinyl octyl ether, vinyl 2-chloroethyl ether, vinyl isobutyl ether, vinyl dodecyl ether, vinyl ctadecyl ether, vinyl phenyl ether, and vinyl cresyl ether. Examples of styrene derivatives include alkylstyrenes, alkoxystyrenes (α-methoxystyrene, p-methoxystyrene etc.) and m-chlorostyrene.

  The reactive monomer may contain other monofunctional radically polymerizable monomers and / or polyfunctional radically polymerizable monomers. Examples of other monofunctional radically polymerizable monomers include vinylphenol, N-vinylcarbazole, 2-vinyl-5-ethylpyridine, isopropenyl acetate, vinyl isocyanate, vinyl isobutyl sulfide, 2-chloro-3-hydroxypropene, Vinyl stearate, p-vinylbenzylethyl carbinol, vinyl phenyl sulfide, allyl acrylate, α-chloroethyl acrylate, allyl acetate, 2,2,6,6-tetramethyl-piperidinyl methacrylate, N, N-diethyl vinyl Carbamate, vinyl isopropenyl ketone, N-vinyl caprolactone, vinyl formate, p-vinyl benzyl methyl carbinol, vinyl ethyl sulfide, vinyl ferrocene, vinyl dichloroacetate, N-vinyl succin Bromide, allyl alcohol, norbornadiene, diallyl melamine, vinyl chloroacetate, N- vinylpyrrolidone, vinyl methyl sulfide, N- vinyl oxazolidone, vinyl methyl sulfoxide, N- vinyl -N'- ethylurea, and include acenaphthalene.

  The various reactive monomers exemplified above can be used alone or in combination of two or more.

The composition for fiber formation contains the reactive monomer described above and a linear or branched second polymer. The second polymer may be a polymer comprising two or more linear chains and a linking group linking the ends of the chains. This polymer contains, for example, a molecular chain represented by the following formula (B). In formula (B), R ²⁰ is a monomer unit constituting a linear chain, n ¹ , n ² and n ³ are each independently an integer of 1 or more, and L is a linking group. Plural R ²⁰ and L in the same molecule may be the same or different.

The linear chain composed of the monomer unit R ²⁰ may be a molecular chain derived from polyether, polyester, polyolefin, polyorganosiloxane, or a combination thereof. Each linear chain may be a polymer or an oligomer.

  Examples of linear chains derived from polyethers include polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains, polyoxybutylene chains and combinations thereof. Polyoxyethylene chains are derived from polyethers such as polyalkylene glycols. Examples of linear chains derived from polyolefins include polyethylene chains, polypropylene chains, polyisobutylene chains and combinations thereof. Linear chains derived from polyester include poly ε caprolactone chains. Linear chains derived from polyorganosiloxanes include polydimethylsiloxane chains. The second polymer can contain these alone or a combination of two or more selected from these.

  The number average molecular weight of each of the linear molecular chains constituting the second polymer is not particularly limited, but may be, for example, 1000 or more, 3000 or more, or 5000 or more, and 80000 or less, 50000 or less, or 20000 It may be the following. In the present specification, number average molecular weight means standard polystyrene equivalent value determined by gel permeation chromatography unless otherwise defined.

  The linking group L is an organic group containing a cyclic group or a branched organic group. The linking group L may be, for example, a divalent group represented by the following formula (30).

R ³⁰ is a cyclic group, a group containing two or more cyclic groups which are bonded directly or via an alkylene group, or contains a carbon atom and is selected from an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom The branched organic group which may contain the hetero atom is shown. Z ⁵ and ^{Z 6 is} a divalent group bonding the ^{R 30} and the linear chain, for example, -NHC (= O) -, - NHC (= O) O -, - O -, - OC ( OO) —, —S—, —SC (= O) —, —OC (= S) —, or —NR ¹⁰ — (R ¹⁰ is a hydrogen atom or an alkyl group). In the present specification, the terminal atom of the linear chain (the atom derived from the monomer constituting the linear chain) is not usually interpreted as the atom constituting the Z ⁵ or Z ⁶ . When it is not clear whether or not the atom at the end of the linear chain is an atom derived from a monomer, the atom may be interpreted as being included in either the linear chain or the linking group.

  The cyclic group contained in the linking group L may contain a hetero atom selected from a nitrogen atom and a sulfur atom. The cyclic group contained in the linking group L is, for example, an alicyclic group, cyclic ether group, cyclic amine group, cyclic thioether group, cyclic ester group, cyclic amide group, cyclic thioester group, aromatic hydrocarbon group, heteroaromatic hydrocarbon It may be a group, or a combination thereof. Specific examples of the cyclic group contained in the linking group L include 1,4-cyclohexanediyl, 1,2-cyclohexanediyl, 1,3-cyclohexanediyl, 1,4-benzenediyl, 1,3- Examples include benzenediyl group, 1,2-benzenediyl group, and 3,4-furandiyl group.

Examples of the branched organic group (for example, R ³⁰ in the formula (30)) contained in the linking group L include a lysinetriyl group, a methylsilanetriyl group, and a 1,3,5-cyclohexanetriyl group.

The linking group L represented by Formula (30) may be a group represented by the following Formula (31). R ³¹ in the formula (31) represents a single bond or an alkylene group. R ³¹ may be an alkylene group having 1 to 3 carbon atoms. The definitions of Z ⁵ and Z ⁶ are the same as in formula (30).

  The weight average molecular weight of the second polymer is not particularly limited, and may be, for example, 5,000 or more, 7,000 or more, or 9,000 or more, or 100,000 or less, 80,000 or less, or 60000 or less. When the number average molecular weight of the second polymer is within these numerical ranges, good compatibility with the other components of the second polymer and good properties of the fibrous molded product can be easily obtained. There is. In the present specification, weight average molecular weight means standard polystyrene equivalent value determined by gel permeation chromatography unless otherwise defined.

  The second polymer can be obtained by a conventional synthetic method using commonly available raw materials as starting materials as understood by those skilled in the art. For example, polyalkylene glycols having reactive terminal groups (such as hydroxyl group), polyesters, polyolefins, polyorganosiloxanes, or a mixture containing these combinations, and reactive functional groups (such as isocyanate groups) and cyclic groups or branched The second polymer can be synthesized by the reaction with a compound having the following group. The second polymer to be synthesized may contain a branched structure based on side reactions such as trimerization of isocyanate groups.

  The composition for fiber formation may contain a polymerization initiator for the polymerization of reactive monomers. The polymerization initiator may be a thermal radical polymerization initiator, a photo radical polymerization initiator, or a combination thereof. Although content of a polymerization initiator is suitably adjusted in a normal range, it may be 0.01-5 mass%, for example based on the mass of the composition for fiber formation.

  Thermal radical polymerization initiators include ketone peroxides, peroxy ketals, dialkyl peroxides, diacyl peroxides, peroxy esters, peroxy dicarbonates, organic peroxides such as hydroperoxides, sodium persulfate, potassium persulfate Persulfates such as ammonium persulfate, 2,2′-azobis-isobutyronitrile (AIBN), 2,2′-azobis-2,4-dimethylvaleronitrile (ADVN), 2,2′-azobis-2 -Azo compounds such as -methylbutyronitrile, 4,4'-azobis-4-cyanovaleric acid, alkyl metals such as sodium ethoxide, tert-butyllithium, 1-methoxy-1- (trimethylsiloxy) -2- Examples thereof include silicon compounds such as methyl-1-propene.

  The thermal radical polymerization initiator may be combined with a catalyst. Examples of the catalyst include metal salts and compounds having reducibility such as tertiary amine compounds such as N, N, N ', N'-tetramethylethylenediamine.

  As a radical photopolymerization initiator, 2, 2- dimethoxy-1, 2- diphenyl ethane 1-one is mentioned. A commercially available product is Irgacure 651 (manufactured by Nippon Ciba-Geigy Co., Ltd.).

  The composition for forming a fiber may contain a solvent or may be substantially free of solvent. The composition for fiber formation may be liquid, semi-solid or solid.

  FIG. 1 is a schematic view showing an embodiment of a method of producing a fibrous molded body. In the method illustrated in FIG. 1, the fiber-forming composition is introduced into the formed elongated flow passage 12 a inside the tubular member 12 from the supply container 10 connected to one end of the tubular member 12. . By irradiating the fiber-forming composition in the flow path 12a with the active ray h 活性 such as ultraviolet rays from the outside of the tubular member 12, the reactive monomer in the molding composition is photoradically polymerized to give the first Form a polymer of The fibrous shaped body 1 cured by the formation of the first polymer is removed from the other end of the tubular member 12. While supplying the composition for fiber formation from the supply container 10, the fibrous molded body 1 can be formed continuously.

  FIG. 2 is also a schematic view showing an embodiment of a method for producing a fibrous molded body. In the method of FIG. 2, the fiber-forming composition in the flow path 12 a is heated by the heating member 14 provided around the tubular member 12. By this heating, the reactive monomer in the composition for fiber formation is thermally radically polymerized to form a first polymer. The heating temperature is not particularly limited, but when the composition for fiber formation contains a solvent, the temperature is preferably equal to or lower than its boiling point.

  Although the flow path 12a shown by FIG.1 and FIG.2 is linear form, the flow path for forming a fibrous molded object is not restricted to this, It may be bent.

  As another method of obtaining a fibrous molded product, a resin molded product having a predetermined shape is produced by generating a first polymer by photoradical polymerization or thermal radical polymerization in a fiber-forming composition filled in any type. A fibrous formed body can also be obtained by a method including a step of obtaining and a method step of cutting out a fibrous formed body from the resin formed body. In this case, the fibrous molded body can be cut out from the resin molded body of a predetermined shape by machining such as cutting and cutting. The resin molding from which the fibrous molding is cut may be, for example, a film.

  In any of the methods, the polymerization of the reactive monomer in the fiber-forming composition is preferably performed under an atmosphere of an inert gas such as nitrogen gas, helium gas, argon gas and the like. For example, when radical polymerization is carried out in the presence of oxygen, the quality of the resulting fibrous shaped article may become unstable due to the inhibition of polymerization by oxygen.

  The fibrous compact obtained by these methods may be further stretched. The fibrous formed body can be easily stretched by pulling while heating the fibrous formed body. Also, a plurality of fibrous shaped articles may be twisted together. The obtained fibrous molded body may be combined with any other fibers to form a plied yarn.

It is believed that when the reactive monomer comprising the radically polymerizable compound of formula (I) is polymerized, a cyclic monomer unit of formula (II) is formed. When the reactive monomer is polymerized in the presence of the first polymer, at least a portion of the cyclic monomer units of formula (II) may form a structure in which the second polymer penetrates the cyclic portion. The following formula (III) schematically shows a structure in which the second polymer (B) penetrates the cyclic portion of the monomer unit of the formula (II) which the first polymer (A) has. R ⁵ in the formula (III) is a monomer unit derived from a reactive monomer other than the radically polymerizable compound of the formula (I). The formation of a structure such as that of the formula (III) forms a cross-linked network structure like a three-dimensional copolymer between the first polymer and the second polymer. In this network structure, it is believed that the freedom of movement of the second polymer penetrating the annular portion is kept relatively high. Such a structure is sometimes referred to by those skilled in the art as a cyclic structure, and the inventors speculate that this contributes to the expression of specific properties such as shape memory property of the fibrous molded body. ing. Although it is not technically easy to directly confirm that a ring moving structure is formed, for example, a stress-strain curve obtained by a tensile test of a fibrous molded product is a so-called J-shaped curve. This suggests the formation of a ring structure. However, the fibrous formed body may not necessarily include such an annular moving structure.

  In the example of formula (III), the second polymer (B) has a plurality of polyoxyethylene chains and a linking group L linking the ends of the chains. Since the linking group L is bulky compared to the polyoxyethylene chain, the state in which the second polymer penetrates the cyclic portion of the monomer unit of the formula (II) is easily maintained like polyrotaxane. The second polymer can be appropriately selected based on the size of cyclic monomer units, the balance such as the inclusion ability, and the properties of polyrotaxane.

  Although the first formed, formed and cured fibrous molded body may or may not have shape memory properties, shape memory can be obtained by appropriately selecting the type of reactive monomer, etc. It is possible to obtain a fibrous molded body having a property. In the present specification, “shape memory property” means that when the fibrous shaped body is deformed by an external force at room temperature (for example, 25 ° C.), the fibrous shaped body holds the deformed shape at room temperature and does not It means the property to return to the original shape when heated to high temperature under load. However, the fibrous formed body may not completely recover the same shape as the original shape by heating. The heating temperature for shape recovery is, for example, 70.degree.

  When the cured fibrous molded body has shape memory, usually, the first polymer is formed and the shape of the fibrous molded body at the time of curing becomes the basic shape. The fibrous shaped body deformed by the external force is deformed so as to approach this basic shape by heating. For example, by curing a fibrous molded body in a flow path having a predetermined shape, a fibrous molded body having a desired shape as a basic shape can be obtained.

  Although the storage elastic modulus at 25 ° C. of the fibrous molded body is not particularly limited, it may be 0.5 MPa or more. The fibrous compact having a storage elastic modulus of 0.5 MPa or more usually has shape memory. The elastic modulus of the fibrous molded body may be 1.0 MPa or more, or 10 MPa or more, or 10 GPa or less, 5 GPa or less, or 500 MPa or less. When the storage elastic modulus is high, there is a tendency that the fibrous molded body can easily maintain the shape after deformation. By having a storage elastic modulus of a suitable size, the fibrous molded product tends to recover its original shape when heated. The elastic modulus of the fibrous molded article can be controlled based on, for example, the type of reactive monomer and the blending ratio thereof, the molecular weight of the second polymer, and the amount of the radical polymerization initiator. The storage elastic modulus of the fibrous molded product itself may be in the above range, or a resin molded product having a predetermined shape (typically a strip shape) for measurement is produced from the composition for forming a fiber, The storage elastic modulus measured using may be in the above range.

  Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to these examples.

1. Synthesis Synthesis Example 1: Synthesis of trans-1,2-bis (2-acryloyloxyethylcarbamoyloxy) cyclohexane (BACH) trans-1,2-cyclohexanediol (2.32 g, 20.0 mmol) in a 100 mL two-necked eggplant flask Were added and the inside of the flask was purged with nitrogen. Dichloromethane (40 mL) and dibutyltin dilaurate (11.8 μL, 0.10 mol%: 0.020 mmol) were placed therein. A solution of 2-acryloyloxyethyl isocyanate (5.93 g, 42.0 mmol) in dichloromethane (4 mL) is dropped from the dropping funnel into the reaction solution in the flask, and the reaction solution is stirred at 30 ° C. for 24 hours to allow the reaction to proceed. The After completion of the reaction, diethyl ether was added to the reaction mixture and the mixture was washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, the solvent was evaporated away under reduced pressure, a solution containing the desired product was isolated from the residue by silica gel chromatography (developing solvent; chloroform), and concentrated. The crude product obtained was purified by recrystallization from diethyl ether and hexane to give white crystals of BACH. The yield was 3.78 g, and the yield was 47.4% by mass.

Synthesis Example 2 Synthesis of PEG-PPG Oligomer To a 20 mL eggplant flask was added polyethylene glycol (PEG 1500, 750 mg, 0.500 mmol, number average molecular weight 1500), and polypropylene glycol (PPG 4000, 2000 mg, 0.500 mmol, number average molecular weight 4000) Then, the inside of the flask was purged with nitrogen, and the contents were melted at 115.degree. To the melt is added 4,4′-dicyclohexylmethane diisocyanate (262 mg, 1.00 mmol), and the melt is stirred at 115 ° C. for 24 hours under a nitrogen atmosphere to obtain PEG-PPG oligomers (polyoxyethylene chains and poly A second polymer containing an oxyproprene chain was obtained.
A GPC chromatogram of the oligomer was obtained at a flow rate of 1 mL / min using 10 mM lithium bromide in DMF (N, N-dimethylformamide) as the eluent. From the obtained chromatogram, the number average molecular weight and the weight average molecular weight of the oligomer were determined as polystyrene conversion values. The weight average molecular weight (Mw) of the oligomer was 9300, and the weight average molecular weight / number average molecular weight (Mw / Mn) of the oligomer was 1.65.

2. Composition Example 1 for Fiber-Forming Composition
BACH of Synthesis Example 1 (55.4 mg, 139.0 μmol), PEG-PPG oligomer of Synthesis Example 2 (69.0 mg, 5.76 μmol), 2-ethylhexyl acrylate (1106 mg, 6.00 mmol), acrylonitrile (780 mg, 6) In a sample bottle, .00 mmol) and Irgacure 651 (31.0 mg, 121.0 μmol) were dissolved by heating to prepare a compound solution (composition for forming a fiber).
Formulation example 2
BACH of Synthesis Example 1 (55.4 mg, 139.0 μmol), PEG-PPG oligomer of Synthesis Example 2 (69.0 mg, 5.76 μmol), 2-ethylhexyl acrylate (1106 mg, 6.00 mmol), acrylonitrile (780 mg, 6) .00 mmol) and benzoyl peroxide (BPO, 3.8 mg, 15.2 μmol) were heated and dissolved in a sample bottle to prepare a compounding solution (fiber-forming composition).

3. Fibrous Molded Article Example 1
The formulation solution of Formulation Example 1 was injected into a glass capillary having a length of 20 cm and an inner diameter of 0.5 mm. The compound solution in the capillary was irradiated with ultraviolet light for 20 minutes at room temperature (25 ° C.) to photoradically polymerize the reactive monomer in the compound solution. The fibrous compact formed by photo radical polymerization was removed from the capillary.

Example 2
The compounded liquid of Formulation Example 1 was placed in a syringe connected to a Naflon (registered trademark) tube having a length of 50 cm and an inner diameter of 1.5 mm. While the mixed solution was fed into the tube at a flow rate of 0.14 mL / min with a syringe pump, the tube portion was irradiated with ultraviolet light to photoradically polymerize the reactive monomer in the mixed solution. The formed fibrous compact was continuously removed from the end of the tube.

Example 3
The mixed solution of Formulation Example 2 was placed in a syringe connected to a Naflon (registered trademark) tube having a length of 100 cm and an inner diameter of 1.5 mm. While feeding the mixed solution into the tube at a flow rate of 0.14 mL / min with a syringe pump, the tube portion was heated in a thermostat of 80 ° C. to thermally radically polymerize the reactive monomer in the mixed solution. The formed fibrous compact was continuously removed from the end of the tube.

Example 4
The fibrous compact obtained in Example 3 was stretched in an atmosphere heated to 80 ° C. to obtain a fibrous compact having an outer diameter of 0.2 mm.

Example 5
The formulation solution of Formulation Example 1 was sandwiched between two release films. The compounded solution was irradiated with ultraviolet light for 20 minutes through a release film to obtain a film-like resin molded product having a thickness of 0.5 mm. From this film, a fibrous shaped product having a width of 0.2 mm was cut out.

DESCRIPTION OF SYMBOLS 1 ... Fibrous molded object, 10 ... Supply container, 12 ... Tubular member, 12a ... Flow path, 14 ... Heating member.

Claims (11)

Formula (I):

A radically polymerizable compound in which X, R ¹ and R ² are each independently a divalent organic group, and R ³ and R ⁴ are each independently a hydrogen atom or a methyl group, and a monofunctional radically polymerizable A first polymer containing a monomer as a monomer unit,
A linear or branched second polymer,
A fibrous molded body containing   The fibrous molded body according to claim 1, wherein the second polymer is a polymer containing a polyoxyalkylene chain.   The fibrous molding according to claim 1, wherein the monofunctional radically polymerizable monomer comprises a compound having a glycidyl group. X in the formula (I) is represented by the following formula (10):

Y is a cyclic group which may have a substituent, and Z ¹ and Z ² are each independently a functional group containing an atom selected from a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom, i The fibrous compact according to any one of claims 1 to 3, wherein j and j each independently represent an integer of 0 to 2, and * represents a bond.   The fibrous molded body according to any one of claims 1 to 4, wherein the weight average molecular weight of the second polymer is 5,000 or more. Formula (I):

A radically polymerizable compound in which X, R ¹ and R ² are each independently a divalent organic group, and R ³ and R ⁴ are each independently a hydrogen atom or a methyl group, and a monofunctional radically polymerizable A reactive monomer containing monomer,
A linear or branched second polymer,
A fiber-forming composition containing   The composition for fiber formation according to claim 6, wherein the second polymer is a polymer containing a polyoxyalkylene chain.   The composition for fiber formation of Claim 6 or 7 in which the said monofunctional radically polymerizable monomer contains the compound which has a glycidyl group. A method of producing a fibrous formed body, comprising a first polymer and a linear or branched second polymer,
The composition for forming a fiber according to any one of claims 6 to 8 is introduced into a long flow path, and photoradical polymerization or heat of the reactive monomer is carried out in the composition for forming a fiber in the flow path. Producing the first polymer by radical polymerization.   The method according to claim 9, further comprising the step of: stretching the fibrous compact removed from the flow channel. A method of producing a fibrous formed body, comprising a first polymer and a linear or branched second polymer,
A process for producing a resin molded product by generating the first polymer by photoradical polymerization or thermal radical polymerization of the reactive monomer in the composition for forming a fiber according to any one of claims 6 to 8,
Cutting out a fibrous molded body from the resin molded body;
A method comprising.

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