JP6446261B2 - Molded body containing syndiotactic polystyrene with functional groups introduced - Google Patents

Description

  The present invention relates to a molded article containing syndiotactic polystyrene having a functional group introduced therein. For example, the present invention relates to a fiber having an ion exchange function capable of efficiently adsorbing and removing useful or harmful metal ions contained in air, water or an organic solvent.

  As a method for adsorbing and removing useful or harmful metal ions contained in air, water or an organic solvent, a method using an ion exchange resin is generally used. The ion exchange resin is a strongly acidic cation exchange resin obtained by sulfonating a copolymer of styrene and divinylbenzene, a weakly acidic cation exchange resin, a strongly basic anion exchange resin, a weakly basic anion exchange resin, There are many types such as amphoteric ion exchange resins and chelate resins.

  Usually, since the shape of an ion exchange resin is a bead shape, there exists a subject that the handleability at the time of replacing | exchanging resin is low. As a product that solves this problem, there is an ion exchange fiber. Ion exchange fibers are easy to process into non-woven fabrics and knits, and are characterized by good handling properties. Furthermore, since the surface area is large and the reaction rate is high compared to bead-shaped ion exchange resins, low-concentration ions can be effectively supplemented, and a large flow rate treatment is possible.

Examples of the ion exchange fiber include polystyrene ion exchange fiber (for example, see Patent Document 1) reinforced with polyolefin in the fiber, polyolefin (PO), polyamide (PA), or ethylene-vinyl alcohol copolymer (EVOH) fiber. Examples include ion exchange fibers and polyvinyl alcohol ion exchange fibers in which ion exchange groups have been introduced by graft polymerization after irradiation.
Moreover, the fiber which provided the ion exchange group by sulfonating resin containing the syndiotactic polystyrene which has the characteristic excellent in heat resistance and chemical resistance is also proposed (for example, refer patent documents 2-4). .

  However, since it is difficult to mold the ion exchange fiber of Patent Document 1 using polystyrene as a fiber, it is necessary to form a sea-island structure fiber using polystyrene as a sea component and polyethylene as an island component, and the molding is complicated. Moreover, there is a concern that the polystyrene part may fall off. Even when the polystyrene part is cross-linked, there is a concern that the fiber strength may decrease due to the occurrence of peeling at the sea-island interface.

  Patent Document 2 discloses a fiber obtained by modifying syndiotactic polystyrene whose glass transition temperature is lowered to 70 to 95 ° C. The glass transition temperature is lowered in order to increase the modification rate, but it is necessary to add a plasticizer. Therefore, there is a concern about problems due to elution of the plasticizer during use. Moreover, since the actual fiber is a core-sheath fiber whose core is polypropylene and whose sheath is syndiotactic polystyrene, the molding is complicated, and there is a concern of peeling at the core-sheath interface. Furthermore, the concentration of sulfur introduced by sulfonation was a maximum of 9.5 ppm, and the ion exchange function was low.

  Patent Document 3 discloses a nonwoven fabric obtained by fiberizing syndiotactic polystyrene and then blending with polyolefin fibers. Even in this technology, polyolefin fibers are essential, which increases the number of manufacturing processes. The concentration of introduced sulfur was as low as 9.3 ppm at the maximum.

  Patent Document 4 discloses that a non-woven fabric formed by mixing syndiotactic polystyrene fibers and polyolefin fibers as easily sulfonated fibers is used as a separator for alkaline batteries. Here, in order to maintain the strength of the nonwoven fabric, it has been shown that a thick fiber is used as the polyolefin fiber, but this causes a problem that the manufacturing process becomes complicated. Moreover, since polyolefin is not sulfonated, there is an upper limit to the degree of sulfonation per unit mass of the nonwoven fabric.

Japanese Patent Laid-Open No. 06-79183 Japanese Patent Application Laid-Open No. 07-278963 JP 07-310265 A JP 11-297293 A

As described above, in the conventional technique, there is a concern of strength reduction due to interfacial peeling in the fiber. In addition, there is a problem that the manufacturing process is complicated because the polyolefin fiber or the like needs strength reinforcement. Furthermore, there is a problem that the amount of polarity (modification amount) introduced into the resulting molded body is low.
Accordingly, an object of the present invention is to provide a molded body that is easy to manufacture and that is highly polar while retaining its shape.

  The present inventor has found that by optimizing the molding conditions and the functional group introduction conditions of the resin containing syndiotactic polystyrene, the functional groups can be introduced at a high level while maintaining the shape of the molded body. In particular, in fiberization, by optimizing the fiberization conditions, resin fibers containing syndiotactic polystyrene can be produced without concern for interfacial delamination and without having to reinforce the strength with polyolefin fibers. The present inventors have found that a modified fiber having a high polarity while maintaining the fiber shape can be obtained by modifying such as sulfonation.

According to this invention, the molded object containing 100-1 mass% of syndiotactic polystyrene into which the functional group was introduce | transduced and 0-99 mass% of thermoplastic resins is provided.
In addition, according to the present invention, a composition containing 100 to 1% by mass of syndiotactic polystyrene and 0 to 99% by mass of a thermoplastic resin is molded, and the functional group is introduced into the syndiotactic polystyrene. Further, a molded product having a functional group introduced after molding is provided.
In the molded article of the present invention, the functional group is preferably an ion exchange group.
Moreover, it is preferable that the thermoplastic resin is compatible with syndiotactic polystyrene before the functional group is introduced.
The thermoplastic resin is preferably at least one selected from atactic polystyrene, styrene elastomer, styrene polymer, and polyphenylene ether.
Moreover, it is preferable that the molded object of this invention is a textile fabric, knitting, a nonwoven fabric, papermaking, or felt.
Moreover, it is preferable that the said functional group is a sulfone group, and sulfur concentration is 50 mass ppm or more.

  ADVANTAGE OF THE INVENTION According to this invention, manufacture is easy and can provide the molded object to which high polarity was provided, maintaining a shape.

  The molded article of the present invention is characterized by containing 100 to 1% by mass of syndiotactic polystyrene (a) having a functional group introduced therein and 0 to 99% by mass of a thermoplastic resin (b).

Syndiotactic polystyrene (a) (hereinafter, syndiotactic polystyrene may be abbreviated as SPS) is a polystyrene polymer mainly having a syndiotactic structure. Here, the syndiotactic structure is a syndiotactic structure, that is, a three-dimensional structure in which phenyl groups that are side chains are alternately located in opposite directions with respect to a main chain formed from carbon-carbon bonds. It is what you have.
The tacticity of SPS is quantified by an isotope carbon nuclear magnetic resonance method ( ^13C -NMR method). The tacticity of the syndiotactic structure can be indicated by the abundance ratio of a plurality of consecutive structural units, for example, a dyad for two, a triad for three, a pentad for five, A polystyrene polymer having a syndiotacticity of preferably 75% or more, more preferably 85% or more for racemic dyad, or preferably 30% or more, more preferably 50% or more for racemic pentad is used.

  SPS includes polystyrene, poly (alkyl styrene), poly (halogenated styrene), poly (halogenated alkyl styrene), poly (alkoxy styrene), poly (vinyl benzoate), and hydrogenated polymers thereof. Is preferably at least one selected from a mixture of two or more selected from these, and a copolymer based on these.

As poly (alkylstyrene), poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (t-butylstyrene), poly (phenylstyrene), poly (vinylnaphthalene), poly (vinyl) Styrene) and the like.
Examples of poly (halogenated styrene) include poly (chlorostyrene), poly (bromostyrene), and poly (fluorostyrene).
Examples of poly (halogenated alkylstyrene) include poly (chloromethylstyrene).
Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).

Among these, preferable styrenic polymers include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p- or t-butylstyrene), poly (p-chlorostyrene), and poly (p-chlorostyrene). (M-chlorostyrene), poly (p-fluorostyrene), hydrogenated polystyrene, and copolymers containing these structural units. Considering that the para-position of styrene is easily modified and an ion exchange group is easily introduced, a homopolymer of styrene (polystyrene) is particularly preferable.
SPS may be used individually by 1 type and may use 2 or more types together.
SPS can be produced according to a known method.

  As the thermoplastic resin (b), a resin having a structural unit that is compatible with the SPS described above is desirable. For example, atactic polystyrene, isotactic polystyrene, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB, SEBC), styrene-butadiene-styrene block copolymer (SBS), Hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), hydrogenated styrene-isoprene-styrene block copolymer (SEPS) and other polymers having a styrene block, and modified products thereof, polyphenylene ether and modified products thereof, styrene-isoprene-styrene block copolymer (SIS), acrylonitrile styrene (AS) resin Acrylonitrile - butadiene - include styrene polymers and styrene-based elastomers such as styrene (ABS) resin.

The molded body of the present invention contains other thermoplastic resin, rubber-like elastic body, compatibilizing agent, various additives, etc., in addition to the above SPS and thermoplastic resin, as long as the characteristics of the present technology are not impaired. May be.
These various additives may be added alone or in combination of two or more.
Other thermoplastic resins include polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); polycarbonate resins; polyphenylene sulfide resins (PPS); polyamides such as nylon 6, nylon 6,6 and nylon 4,6 Resins; Polyether resins such as polyphenylene oxide, polysulfone, and polyethersulfone; Acrylic resins such as polyacrylic acid, polyacrylic acid ester, and polymethyl methacrylate; Polyethylene, polypropylene, polybutene, poly-4-methylpentene-1, and ethylene Polyolefin resins such as propylene copolymer, ethylene-acrylic acid copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer; polyvinyl chloride, polyvinylidene chloride, polyethylene Halogen-containing vinyl compound polymer such as vinylidene fluoride; polyoxymethylenes; polyvinyl alcohol resins; and derivatives thereof.
These other thermoplastic resins may be used individually by 1 type, and may use 2 or more types together.

Examples of rubber-like elastic bodies include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene (registered trademark), polysulfide rubber, thiocol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, ethylene propylene rubber (EPM). ), Ethylene-propylene diene rubber (EPDM), and core-shell type particulate elastic bodies such as siloxane-containing core-shell rubbers including methyl methacrylate-butyl acrylate-siloxane, or rubbers modified from these.
These rubber-like elastic bodies may be used alone or in combination of two or more.

Examples of the compatibilizing agent include a polymer having compatibility or affinity with SPS and a thermoplastic resin or rubber-like elastic body and having a polar group. Specifically, rubbers modified with acid anhydrides such as maleic anhydride modified SEBS, maleic anhydride modified SEPS, maleic anhydride modified SEB, maleic anhydride modified SEP, maleic anhydride modified EPR, styrene-maleic anhydride copolymer Polymer (SMA), styrene-glycidyl methacrylate copolymer, terminal carboxylic acid-modified polystyrene, terminal epoxy-modified polystyrene, terminal oxazoline-modified polystyrene, terminal amine-modified polystyrene, sulfonated polystyrene, styrene ionomer, styrene-methyl methacrylate graft polymer, (Styrene-glycidyl methacrylate) -methyl methacrylate graft polymer, acid-modified acrylic-styrene-graft polymer, (styrene-glycidyl methacrylate) -styrene graft poly -, Polybutylene terephthalate-polystyrene graft polymers, and modified styrenic polymers such as maleic anhydride modified syndiotactic polystyrene, fumaric acid modified syndiotactic polystyrene, glycidyl methacrylate modified syndiotactic polystyrene, amine modified syndiotactic polystyrene, etc. , (Styrene-maleic anhydride) -polyphenylene ether graft polymer, maleic anhydride-modified polyphenylene ether, fumaric acid-modified polyphenylene ether, glycidyl methacrylate-modified polyphenylene ether, amine-modified polyphenylene ether, and the like.
These compatibilizers may be used alone or in combination of two or more.

  Examples of the various additives include antioxidants, nucleating agents, plasticizers, mold release agents, flame retardants, flame retardant aids, pigments, dyes, carbon black, and antistatic agents. What is necessary is just to mix | blend a well-known thing each as needed. Moreover, an additive may be used individually by 1 type and may use 2 or more types together.

The content rate of SPS (a) in a molded object is 1-100 mass%. When the SPS content is less than 1% by mass, a desired modification rate cannot be obtained, and the strength of the molded product is further reduced. For example, in the case of fibers, the strength of the fibers may be reduced. The content of SPS is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass.
The content rate of the thermoplastic resin (b) in a molded object is 0-99 mass%. Preferably it is 0-50 mass%, More preferably, it is 0-20 mass%, Most preferably, it is 0-10 mass%.

The total amount of SPS (a) and thermoplastic resin (b) in the entire molded body is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. preferable.
In addition, the molded object may consist only of SPS (a) and a thermoplastic resin (b).

  Examples of the functional group introduced into the SPS include a sulfone group, a chlorosulfone group, a nitro group, a chloromethyl group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an isocyanate group, an amino group, and an aldehyde group.

  The functional group introduced into SPS is preferably an ion exchange group. The ion exchange group is not particularly limited, and those widely used can be used. For example, sulfone group, carboxyl group, phosphate group, amino group, methylamino group, secondary ammonium group such as ethylamino group, tertiary ammonium group such as dimethylamino group, diethylamino group, trimethylammonium group, dimethylethanol Examples thereof include a quaternary ammonium group such as an ammonium group and a coordination group that forms a chelate such as a polyamine group.

As a technique for introducing a functional group into SPS, a known polystyrene modification technique can be used. For example, a sulfone group can be introduced by reaction of polystyrene and sulfuric acid. A chlorosulfone group can be introduced by reaction with chlorosulfonic acid. Nitro groups can be introduced by reaction with nitric acid. A chloromethyl group can be introduced by reacting with chloromethyl ether using aluminum chloride or tin tetrachloride as a catalyst. Since SPS introduced with a chloromethyl group has high reactivity of chlorine at the benzyl position, it can be converted into various derivatives. For details, refer to “Polymer Synthetic Chemistry (Tokyo Denki University Press) pp. 323-325”.
Further, a quaternary ammonium group can be introduced by chloromethylation with methyl chloromethyl ether or the like and then amination with trimethylamine or dimethylethanolamine. Primary and secondary amino groups can be introduced by amination with diethylenediamine or the like.

In addition, it is also possible to introduce | transduce the functional group which has functions other than ion exchange by using the said method. For example, it is possible to give SPS a function of adsorbing and removing bacteria, E. coli, viruses, proteins, harmful organic substances, and the like.
In addition, the introduction of the functional group facilitates processing using the functional group on the surface of the molded body, such as dyeing with dyes, printing with general ink, plating, various coatings, and improvement of adhesion.

  Hereinafter, the case where a sulfone group is introduced into SPS will be described. There is no restriction | limiting in particular about the method of introduce | transducing a sulfone group into SPS, A well-known method is applicable. For example, a method of immersing SPS in concentrated sulfuric acid (for example, 98% or more) at 10 to 80 ° C. can be mentioned. When the denaturation conditions are severe, for example, when the immersion temperature exceeds 80 ° C., the introduction of polar groups becomes excessive and the affinity with water and the denaturing material is improved, but the SPS molecules are cut, etc. The body shape may not be maintained. On the other hand, when the modification conditions are mild, for example, when the immersion temperature is less than 10 ° C., modification takes time, which is not desirable from the viewpoint of productivity. Therefore, the immersion temperature is preferably 20 to 70 ° C, more preferably 30 to 60 ° C, and particularly preferably 40 to 50 ° C.

  The time during which SPS is immersed in concentrated sulfuric acid (reaction time) can be appropriately adjusted depending on the immersion temperature. Usually, it is about 1 minute to 120 minutes, and preferably 10 minutes to 60 minutes.

  Also preferred is a method in which SPS is contacted with a sulfonating agent in the presence of an organic solvent. By bringing the SPS and the sulfonating agent into contact with each other in the presence of an organic solvent, it becomes possible to introduce a desired amount of the sulfone group while suppressing the sulfonating agent from coming into direct contact with the SPS and deteriorating.

  As the sulfonating agent, for example, a known sulfonating agent such as chlorosulfonic acid, fuming sulfuric acid, sulfur trioxide, sulfur trioxide-triethyl phosphate, concentrated sulfuric acid, trimethylsilyl chlorosulfate or the like is preferably used. From the viewpoint of industrial availability and ease of introduction of sulfone groups, it is preferable to use chlorosulfonic acid alone or a mixture containing chlorosulfonic acid.

  The organic solvent is preferably one that does not decompose the sulfonating agent, does not inhibit introduction of the sulfone group, and does not cause degradation such as decomposition of SPS or the thermoplastic resin constituting the molded body. Specifically, a halogenated hydrocarbon is preferable. Examples of the halogenated hydrocarbon include dichloromethane, 1,2-dichloroethane, chloroform, 1-chloropropane, 1-chlorobutane, 2-chlorobutane, 1,4-dichlorobutane, 1-chloro-2-methylpropane, and 1-chloro. Examples include pentane, 1-chlorohexane, chlorocyclohexane, and the like. In particular, an organic solvent containing at least one selected from the group consisting of dichloromethane, 1,2-dichloroethane and 1-chlorobutane is preferable.

The amount of the sulfonating agent used is preferably 0.1 to 100 times (mass ratio), more preferably 0.5 to 50 times (mass ratio) with respect to SPS. If it is in the said numerical range, the introduction amount of a sulfone group will become a suitable range. Moreover, it is possible to prevent the SPS from being chemically deteriorated.
The concentration of the sulfonating agent in the organic solvent may be appropriately set in consideration of the target introduction amount of the sulfone group and reaction conditions (temperature, time, etc.). Specifically, it is preferably 0.05% by mass or more and 20% by mass or less, and more preferably 0.2% by mass or more and 10% by mass or less. If it is in the range of 0.05% by mass or more and 20% by mass or less, the sulfonating agent and the benzene ring of the SPS can easily come into contact with each other, a desired amount of sulfone group can be introduced, and the introduction time can be short. In addition, the introduction of the sulfone group becomes uniform.

The reaction temperature for bringing the SPS into contact with the sulfonating agent is not particularly limited, but is preferably 0 ° C. or higher and 100 ° C. or lower, more preferably 10 ° C. or higher and 30 ° C. or lower. If reaction temperature is 0 degreeC or more, it can prevent taking time more than necessary for reaction. Moreover, if it is 100 degrees C or less, reaction can be adjusted appropriately, generation | occurrence | production of a side reaction can be prevented and the problem of reducing the characteristic of a film | membrane can be avoided. In addition, since it is not necessary to use a pressure-resistant container, it is preferable that reaction temperature is below the boiling point of the organic solvent to be used.
Moreover, since heating and cooling are unnecessary if the reaction temperature is set to a temperature close to room temperature, heating equipment and cooling equipment can be eliminated.

  Further, the reaction time when the SPS and the sulfonating agent are brought into contact with each other is not particularly limited, and can be determined, for example, by the amount of the sulfone group to be introduced. Generally, 0.5 hours or more is preferable, and 2 hours or more is more preferable. On the other hand, the upper limit of the reaction time is preferably 100 hours or less. When the reaction time is 0.5 hour or more, the contact between the sulfonating agent and SPS is sufficient, and a desired amount of the sulfone group can be introduced. Moreover, if reaction time is 100 hours or less, productivity will not be impaired. The reaction conditions may be appropriately set in consideration of the reaction atmosphere such as the sulfonating agent and organic solvent used, the target production amount, and the like.

  When the functional group is a sulfone group, the sulfur concentration in the molded body is preferably 50 mass ppm or more. When the sulfur concentration is 50 ppm or more, the capacity as an ion exchange material is satisfied. The sulfur concentration is preferably 100 ppm by mass or more, more preferably 500 ppm by mass or more, and most preferably 1000 ppm by mass or more.

  In addition, as a method for controlling the introduction amount of the functional group, for example, a monomer ratio may be prepared in an SPS made of a copolymer of styrene and a para-alkylated styrene such as para-methylstyrene.

  The molded article of the present invention is obtained by molding an SPS before introducing a functional group, or a resin composition containing an SPS before introducing a functional group and a thermoplastic resin (b), and then the obtained molded article. It is preferable to manufacture by introducing a functional group into the SPS therein. Moreover, you may manufacture by shape | molding the resin composition containing SPS (a) into which the said functional group was introduce | transduced, or SPS (a) into which the functional group was introduced, a thermoplastic resin (b), etc. . Hereinafter, the raw material before molding is collectively referred to as a starting raw material regardless of whether or not a functional group is introduced into the SPS.

The method for producing a molded body from the starting material is not particularly limited. Depending on the product shape, it can be appropriately selected from known molding techniques such as injection molding, extrusion molding, press molding, and melt spinning.
There is no restriction | limiting in particular as a molded object, For example, fibrous molded objects, such as a fiber, a woven fabric, a knitted fabric, a nonwoven fabric, papermaking, a felt, injection molded products, powder, flakes, a film, etc. are mentioned. Among these, from the aspect of making the best use of the moldability of SPS and further making the best use of the ion exchange capacity, as an ion exchange membrane that is a film-like molded body or an ion-exchange fiber that is a fibrous shaped body Utilization is preferable, and utilization as an ion exchange fiber is particularly preferable.

  In the case of a fibrous molded body, the functional group may be introduced into the spun fiber and then processed into a final shape such as woven fabric, knitted fabric, non-woven fabric, papermaking or felt, or after the fiber has been processed into the final shape. A functional group may be introduced. Hereinafter, as an example of the molded body, a fiber and a fibrous molded body obtained by processing the fiber will be described.

There is no particular limitation on the method for processing the starting material into fibers, and examples thereof include known melt spinning methods such as a multifilament method, a spunbond method, a melt blow method, and a monofilament method. In order to obtain a fiber having excellent strength, in the present invention, it is preferable to perform melt spinning under the conditions described in JP-A-2014-111852. This manufacturing method has a spinning process and a drawing process.
In the spinning step, the melting temperature (extrusion temperature of the extruder) is at least equal to or higher than the melting point of the starting material SPS, and is usually equal to or higher than the temperature at which the SPS completely melts. From the viewpoint of avoiding poor melting and suppressing the decomposition of SPS, the temperature is preferably 280 to 330 ° C, more preferably 300 to 320 ° C.
After the fibers extruded from the extruder nozzle are cooled, they are wound on a winder that is spaced enough to allow the fibers to solidify sufficiently. The method for cooling the fiber extruded from the nozzle is not particularly limited, and may be air-cooled or a coolant such as water may be used. The cooling temperature is usually preferably 0 to 40 ° C, more preferably 0 to 30 ° C.

The winding speed by the winder, that is, the set spinning speed preferably satisfies the following formula (1), and more preferably satisfies the following formula (2).
V <Vmax = −2.5 × D + 653 (1)
[V: A set spinning speed (m / min) when the molten resin discharged from the nozzle is wound by a winder.
Vmax: the maximum spinning speed (m / min) that can be drawn with respect to the set spinning speed V.
D: The ratio of the discharge rate of the resin extruded from the nozzle and the speed of the fiber wound by the winder, which is expressed by the following formula (a) [may be referred to as draft ratio. ].
D = V × ρ × πR ² ÷ M (a)
(V: Spinning speed set when the molten resin discharged from the nozzle is wound by a winder (r / m), ρ; Density (g / cm ³ ), R: Nozzle radius (mm), M: Single hole discharge amount (G / min))]
V <Vmax = −3.6 × D + 366 (2)
(In Formula (2), V, Vmax, and D are the same as those in Formula (1).)

  The set spinning speed (V) is usually preferably 30 to 600 m / min, more preferably 40 to 500 m / min, and still more preferably 50 to 450 m / min. If the set spinning speed is too slow, the productivity is not only poor, but the orientation does not take place. If the spinning speed is too fast, the crystallization associated with the orientation proceeds too much and the stretchability becomes poor. As indicated by the formula (a), the nozzle radius and the discharge amount can be adjusted so that the set spinning speed satisfies the formula (1) or (2).

In formula (a), the density (ρ) is the density of SPS (for example, about 1.04 g / cm ³ ). The nozzle radius (R) is preferably 0.05 to 0.5 mm, more preferably 0.1 to 0.5 mm, from the viewpoint of preventing the drawable magnification from becoming low. The single hole discharge amount is preferably 0.2 to 3 g / min, more preferably 0.3 to 2.5 g / min, and still more preferably 0.4 to 2.0 g / min.

  The starting material of the fiber includes various additives usually used for improving spinnability, workability, durability, etc., for example, heat resistance stabilizer, antioxidant, crystal nucleating agent, light resistance stability. 1 type or 2 or more types, such as an agent, an antioxidant, a lubricant, a smoothing agent, a pigment, a water repellent, an oil repellent, a concealing agent such as titanium oxide, a gloss imparting agent, a flame retardant, and a plasticizer. Good. There is no restriction | limiting in particular in the addition amount, What is necessary is just to add in the ratio of 0.01-10 mass parts with respect to 100 mass parts of resin components, Preferably it is 0.02-5 mass parts.

The fiber (unstretched fiber) wound by the winder in the spinning process is stretched by a stretching machine. It may be stretched as it is from the spinning line, or may be stretched after being wound once.
The fiber is stretched while being heated. There is no restriction | limiting in particular in the heating drawing method of a fiber, A well-known method is employable. For example, (i) a method of performing heat stretching using a heat roll or a hot plate with a general heat stretching machine or the like, and (ii) heat stretching with laser irradiation with a laser heating stretching machine or the like (hereinafter abbreviated as laser stretching). And (iii) a method of drawing high temperature steam while heating the fiber with a steam drawing machine or the like. Among these, the methods (i) and (ii) are preferable.

  In the method (i), the heating temperature during hot roll stretching (the roll temperature when using a hot roll, the plate temperature when using a hot plate) is preferably not less than the glass transition temperature of SPS and not more than 150 ° C. 110 ° C. or higher and 130 ° C. or lower is more preferable, and 110 ° C. or higher and 120 ° C. or lower is further preferable. If the glass transition temperature is higher than the glass transition temperature of SPS, which is the main component, it is possible to prevent the resin from becoming hard and difficult to be deformed. If the temperature is 150 ° C. or lower, the yarn does not soften too much, so that it can be prevented from being melted or wound around a hot roll or the like.

  Further, the stretching ratio can be increased by laser stretching as in method (ii). At the time of laser drawing, a drawn fiber can be obtained by adjusting the laser output according to the draw ratio so that the yarn does not whiten or break. In the present invention, the output of the laser is preferably 1 to 30 W, more preferably 1 to 20 W, and even more preferably 3 to 20 W.

  Stretching is performed at a stretching ratio of 2.6 times or more. A fiber having good tensile properties can be obtained by stretching at a stretching ratio of 2.6 times or more. From the same viewpoint, the draw ratio is preferably 3.4 times or more, more preferably 4.0 times or more. The upper limit of the draw ratio is not particularly limited, but if the draw ratio is increased too much, thread breakage may occur or the fiber may be whitened due to crazing, so the upper limit is preferably 6.0 times. More preferably, it is 5.5 times, still more preferably 5.0 times.

The fiber production conditions are more preferably conditions for stretching the fiber obtained at a set spinning speed satisfying the above formula (2) to about 4.0 to 5.0 times. However, even better fibers can be obtained.
Further, the set spinning speed is set to the formula (2), and the film can be stretched to 4.0 times or more (preferably about 4.0 to 5.0 times) by laser stretching.

The single yarn thickness of the yarn may be the same or different, and is preferably in the range of 0.5 to 8 dtex, for example. The strength of the single yarn is also preferably 2.0 cN / dtex or more, and more preferably 2.5 cN / dtex or more. When it is 2.0 cN / dtex or more, for example, there is an advantage that production stability is improved, for example, yarn breakage is reduced during weaving in the weaving process of the fabric. When the tensile strength is less than 2.0 cN / dtex, yarn breakage frequently occurs during weaving, and the practical strength of the resulting industrial fabric is also lowered.
Further, the cross-sectional shape of the single yarn of these fibers may be appropriately selected within a range that does not hinder the production of the fabric and the physical properties of the obtained fabric, such as a circle, an ellipse, a flat, a polygon, a hollow, and other irregular shapes. Moreover, you may use what integrated several thread | yarn with different thickness, cross-sectional shape, etc. by the combined yarn, the twist, etc. Furthermore, it may be subjected to processing such as twisting, bulking, crimping, winding, gluing, etc. The form of the yarn is not only long fiber filaments but also short fiber spun yarns, composite yarns thereof. Etc. may be used.
Alternatively, a method of obtaining fine fibers by dissolving and removing the sea component from the sea-island composite fiber having the island component as a starting material and a sea component as a polymer that is more soluble than the island component may be used. In this case, a method is preferred in which the sea-island type composite fiber is melt-spun and then drawn and then dissolved and removed. Moreover, you may make it a nonwoven fabric after shortening a fine fiber.
In addition, it is preferable that it is a single fiber from a viewpoint which can simplify a manufacturing method.

The nonwoven fabric can be produced, for example, by forming a fiber web (before entanglement or bonding of the nonwoven fabric) from the fibers and processing the nonwoven fabric.
As a method for forming a fiber web from fibers, for example, a dry method such as a card method or an air lay method, a wet method, a spun bond method, a melt blow method and the like are suitable. In addition, when forming a fiber web by the card method, since the difference in strength between the warp direction and the transverse direction is small if the fibers include crossing orientation directions, a suitable fiber web can be obtained. When used, fine fibers are easily obtained.

  As a method of forming a nonwoven fabric from a fiber web, for example, a method of entanglement of a fiber web by the action of a water flow or a needle, a method of fusing and bonding the heat-fusible components of the fiber, a method of binding by a binder, Or there is a method of combining these methods. The fiber web obtained by the spunbond method or the melt blow method may be used as a non-woven fabric as it is.

As an entanglement method by this water flow, for example, a nozzle diameter of 0.05 to 0.3 mm, more preferably 0.10 to 0.18 mm, a pitch of 0.2 to 3 mm, and more preferably 0.4 to 1. Using a nozzle plate arranged in a row at 2 mm or a nozzle plate in which nozzles are arranged in two or more rows such as a lattice shape or a staggered shape, with a water flow of 1-30 MPa (10-300 kg / cm ² ), the fiber web Process from one or both sides. There is no restriction | limiting in particular in the thickness of the fiber sheet-like material obtained as mentioned above, The thing of various thickness can be used according to the objective.

  In addition, a wet method such as a chemical bond, a thermal bond, a needle punch, a spun lace, a stitch bond, a paper making method, a water punch method, or the like can be used as a method for manufacturing the nonwoven fabric.

  In the nonwoven fabric of this invention, although the fiber which is the molded object of this invention is used, you may use another fiber with this as needed. For example, nylon fibers such as 6-nylon and 66-nylon, ethylene-vinyl alcohol copolymer fibers, polyester fibers such as polyethylene terephthalate and polytrimethylene terephthalate, liquid crystal polymer (LCP) fibers, aramid fibers, Polypropylene, polyethylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-butene-propylene copolymer and other polyolefin fibers may be blended or laminated.

There is no restriction | limiting also about the cross-sectional shape of the fiber used for a nonwoven fabric, The fiber which has various cross sections can be used with a well-known method. For example, in a fiber cross section, a concentric or eccentric core-sheath type, a chrysanthemum type in which one component 1 is arranged between other components 2, or a multilayer in which one component 1 and another component 2 are alternately laminated in two or more layers The type can be used.
Although it is essential that a resin composition containing SPS is present on at least a part of the surface of the fiber, for example, in the case of a core-sheath fiber, there is no limitation on the resin used for the core portion. For example, nylon materials such as 6-nylon and 66-nylon, ethylene-vinyl alcohol copolymers, polyesters such as polyethylene terephthalate and polytrimethylene terephthalate, liquid crystal polymer (LCP), aramid, polypropylene, polyethylene, polybutene And polyolefins such as polymethylpentene, ethylene-propylene copolymer, and ethylene-butene-propylene copolymer. From the viewpoint of improving the interfacial strength of the core-sheath fiber, it is also possible to adopt a material that is compatible with the material that constitutes the core and the material that constitutes the sheath, and the material that constitutes the core and the material that constitutes the sheath, It is also possible to add common materials.
The nonwoven fabric is preferably not mixed with other fibers. This is because, if mixed with other fibers, if functional groups cannot be introduced into other fibers, the amount of functional groups introduced in the entire nonwoven fabric is reduced.

In order to form a woven fabric from fibers, a commonly used technique such as plain weave, oblique weave, lattice weave, twill weave, knot weave, tangle weave, imitation weave, or a composite structure thereof can be used. If necessary, in addition to the two axes of warp and weft, a multi-axis design including an oblique direction (for example, 60 degrees direction) may be used. Of these, plain weaving is preferable in that the denseness of the structure, the uniformity of physical properties and performance can be ensured.
For the production of the woven fabric, various looms used for weaving ordinary industrial woven fabrics may be appropriately selected. For example, a shuttle loom, a water jet loom, an air jet loom, a rapier loom, a projectile loom or the like can be used.

  In order to form a knitted fabric from fibers, a commonly used knitting method can be used. For example, a single knitted fabric such as a single knitted fabric such as a single tricot knitting, a single cord knitting, a single atlas knitting, a weft knitting such as a flat knitting, a rubber knitting, a pearl knitting or the like, or a double knitting structure obtained by combining them Is mentioned.

  When the molded body is a film, it may be an unstretched film or sheet, but it is possible to use a film whose mechanical properties such as strength have been improved by uniaxial stretching or biaxial stretching, after the functional group has been added. It is preferable in terms of maintaining the shape. In this case, the functional group may be imparted before or after stretching, or after the heat setting step. From the viewpoint of the introduction efficiency of the functional group, the reaction before stretching is preferable, and from the viewpoint of productivity, it is preferable to perform the reaction after stretching and simultaneously collect the reaction solvent during heat setting.

  In the molded product of the present invention, heat treatment (annealing) may be performed in order to improve the crystallinity of the molded product. In this case, the temperature can be set between the glass transition temperature of the SPS and the melting point. Specifically, it is 90-270 degreeC, Preferably, it is 100-240 degreeC, More preferably, it is 100-220 degreeC, Most preferably, it is 120-180 degreeC, Most preferably, it is 140-170 degreeC.

The following three types were used as SPS.
・ SPS-1
Syndiotactic polystyrene (made by Idemitsu Kosan Co., Ltd., Zalec 90ZC: 300 ° C., MFR at a load of 1.2 kg is 9 g / 10 min)
The mass average molecular weight measured by gel permeation chromatography at 135 ° C. using 1,2,4-trichlorobenzene as a solvent is 200,000. Moreover, melting | fusing point by DSC measurement is 271 degreeC.
It was confirmed by measurement of ¹³ C-NMR that SPS-1 was a polystyrene having a syndiotactic structure.

・ SPS-2
Syndiotactic polystyrene (made by Idemitsu Kosan Co., Ltd., Zarek 300ZC: 300 ° C., MFR at a load of 1.2 kg is 30 g / 10 min)
The mass average molecular weight measured in the same manner as SPS-1 was 140,000, and the melting point was 271 ° C.
SPS-2 was confirmed to be syndiotactic polystyrene by ¹³ C-NMR measurement.

・ SPS-3
Syndiotactic polystyrene (made by Idemitsu Kosan Co., Ltd., Zalec 142ZE: MFR at 300 ° C. and a load of 1.2 kg is 14 g / 10 min)
The mass average molecular weight measured in the same manner as SPS-1 was 170,000, and the melting point was 246 ° C.
It was confirmed by measurement of ¹³ C-NMR that SPS-3 was a polystyrene with a syndiotactic structure.

[fabric]
Examples 1-3
(1) Production of plain fabric After the SPS-1 was dried in a vacuum dryer at 80 ° C. for 5 hours, using a twin screw extruder with a screw diameter of 30 mm, the cylinder and gear pump temperature was 290 ° C., and the nozzle temperature was 320 ° C. SPS-1 was melted and extruded from a nozzle with a φ0.7 mm hole at a single hole discharge rate of 0.168 g / min. The extruded SPS-1 was wound at a roll temperature of 115 ° C. and a winding speed of 380 m / min, and drawn at a draw ratio of 2 to produce a drawn fiber having a yarn diameter of 2 dtex.
The obtained drawn fiber, was confirmed melting behavior by DSC, the difference [Delta] H _TCC and [Delta] H _f was 32.0cal / g.
Measurement condition:
Using a DSC apparatus (DSC-7 manufactured by PerkinElmer Co., Ltd.), the temperature was raised from room temperature to 20 ° C./min, and the observed absolute value of low-temperature crystallization enthalpy (ΔH _TCC ) and the absolute value of melting enthalpy (ΔH _f ) was measured.
When the difference between ΔH _TCC and ΔH _f is less than 1 cal / g, the obtained fiber is determined to be amorphous, and there is a possibility that problems such as shrinkage at high temperatures may occur.
The produced drawn fiber was cut into a length of 51 mm and twisted to obtain a spun yarn having a cotton count of 12/1. A plain weave fabric was woven using the spun yarn thus obtained to obtain a plain fabric having a warp density of 45 / 2.54 cm and a cotton yarn density of 36 / 2.54 cm.

(2) Sulfonation of plain woven fabric A 10 g sample was taken from the obtained plain woven fabric. 125 mL of sulfuric acid (reagent: Aldrich product, product number V8400041, grade VETEC AR, purity ≧ 98%) was placed in a flask and heated to the temperature shown in Table 1. After raising the temperature, the sample was put into a flask and stirred for the time shown in Table 1. Thereafter, the contents of the flask were poured into 500 mL of ice water to stop the reaction. Thereafter, filtration was performed, and the sample was washed with water (200 mL) on a filter paper.
The obtained sample was stirred in water (500 mL) for 5 minutes or longer, then filtered, and washed with water on a filter paper (200 mL) for a total of 3 times. In addition, it was confirmed that the washing liquid in the third washing operation was neutral and sufficiently washed.
The obtained sample was dried at 80 ° C. under reduced pressure for 6 hours.

Table 1 shows the reaction temperature at the time of sulfonation, the reaction time, and the sulfur concentration and shape of the sample after sulfonation.
The sulfur concentration in the sample was measured with a sulfur analyzer (EMIA-920V2 manufactured by Horiba, Ltd.) using a high frequency induction heating combustion-infrared absorption method.
The evaluation of the shape was as follows.
◯: The shape of the molded body before modification was maintained. Δ: The shape of the molded body was partially deformed before and after modification. ×: The sample was dissolved or dispersed in the solution, and the sample could not be taken out. That is, the sulfonated molded product could not be recovered.

[Production of non-woven fabric]
Examples 4 to 9, Comparative Examples 1 and 2
(1) Production of Nonwoven Fabric As a starting material, the above SPS-2 or SPS-3 and polystyrene (HF77 manufactured by PS Japan) were mixed and used at the composition ratio shown in Table 2.
After starting material was dried in a vacuum dryer at 80 ° C. for 5 hours, using a twin screw extruder with a screw diameter of 35 mm, the material was melted at a cylinder and gear pump temperature of 300 ° C. and a nozzle temperature of 320 ° C. Extrusion was performed at a single hole discharge rate of 0.12 g / min from a nozzle having a diameter of 0.36 mm and 301 holes. The extruded molten resin is further pulled and thinned by an air flow of 300 Nm ² / hrs and 300 ° C., and the nonwoven fabric (weight per unit: based on the condition of a conveyor speed of 7 m / min and a distance between the die and the conveyor of 100 mm). 20 g / cm ² ) was produced.
The nonwoven fabric obtained in Example 4-6, was confirmed melt behavior by DSC in the same manner as in Example 1, the difference [Delta] H _TCC and [Delta] H _f was 12.4cal / g. When the difference between ΔH _TCC and ΔH _f is less than 1 cal / g, the obtained non-woven fabric fiber is judged to be amorphous, and there is a risk of problems such as shrinkage at high temperatures.

(2) Sulfonation of the nonwoven fabric Except that the reaction temperature and time were set as shown in Table 2, they were sulfonated and evaluated in the same manner as the woven fabric described above. The results are shown in Table 2.

[Annealed nonwoven fabric]
Examples 10 to 15 and Comparative Example 3
A nonwoven fabric was produced in the same manner as in Example 4 except that the composition ratio of the starting materials, the reaction temperature and the reaction time were as shown in Table 2. The obtained nonwoven fabric was annealed at 150 ° C. for 10 minutes. Note that [Delta] H _TCC nonwoven obtained in Examples 10 to 12 are not confirmed, the value of [Delta] H _f was 22.2cal / g.
Except having set reaction temperature and time as shown in Table 2, it sulfonated and evaluated like the textile mentioned above. The results are shown in Table 2.

The molded body of the present invention can be used for, for example, applications of ion exchange membranes, ion exchange resins, and filters. Specifically, liquid filters such as water and organic solvents, treatment membranes, exhaust gas purification filters, chemical filters, seawater concentration, separators for fuel cell electrolyte membranes and alkaline batteries, medical filters such as dialyzers, food and pharmaceuticals It is preferably used for industrial process filters, recovery of useful substances, harmful substances or metals from contaminated water and waste liquid, pure water production, synthesis catalysts such as acid catalysts, and the like.
In particular, when the molded body is a fiber, woven fabric, knitted fabric, non-woven fabric, papermaking, or felt, it is particularly preferable because useful and harmful substances can be adsorbed and removed efficiently and replacement work is easy.

Claims (9)

Sulfone group is introduced, including single yarn comprising a 0-50 wt% syndiotactic polystyrene 100-50 wt% and the thermoplastic resin, a fibrous molded body. The fibrous shaped product according to claim 1, wherein the thickness of the single yarn is 0.5 to 8 dtex. The fibrous shaped product according to claim 2, wherein the strength of the single yarn is 2.0 cN / dtex or more. The fibrous molded object in any one of Claims 1-3 with which the said thermoplastic resin is compatible with the syndiotactic polystyrene before introduce | transducing the said sulfone group. The fibrous molded body according to any one of claims 1 to 4 , wherein the thermoplastic resin is at least one selected from atactic polystyrene, a styrene elastomer, a styrene polymer, and polyphenylene ether. The fibrous molded body according to any one of claims 1 to 5 , wherein the sulfone group is introduced after molding. Fibrous it molded body according to any one of claims 1 to 6 sulfur concentration is more than 50 mass ppm. A method of manufacturing a fibrous molded article according to any one of claims 1 to 7
The fibrous shaped body comprising a single yarn comprising a 0-50 wt% syndiotactic polystyrene 100-50 wt% and a thermoplastic resin, comprising the step of immersing at 20 to 70 ° C. in concentrated sulfuric acid method. The manufacturing method according to claim 8 , wherein the immersion time in the concentrated sulfuric acid is 1 to 120 minutes.