Stimuli-responsive material and medical material comprising same

Technical Field

The invention relates to the stimulus responsive material, and in more detail, relates to comprises a stimulus responsive polymer, fiber and water the stimulus responsive material, and medical material using the same.

Background Art

Through the external heat, light, current, electric field, such as pH or state and changes in the volume (swell, shrink) the stimulus responsive polymer is usually known, and has been tried is used as a functional material of the various fields. It is proposed as, for example, drug carrier or adhesion material, such as the pharmaceutical delivery system of the medical material, cosmetics, the movable part of the robot is driven high molecular actuator, chemical valve, substance separation, and attention to the optical element or the like. In particular, medical material of this kind of material is considered to be the use of a.

Adhesion is in inflammation, trauma, abrasion, trauma or the like in operation in the, in the process of healing of the wound around with the organ or organization of the form. For example, in various surgical excision of often takes place in the affected part, and of the injury part of the repair, and the like, at this moment the adhesion after operation will occur. In order to prevent this kind of adhesion, as during wound healing in vivo substances play a barrier function, such as are known to "Seprafilm" (Genzyme society system   Biosugry) or "Interseed" (  &   Johnson society system Johnson) a sheet such as the anti-adhesion material.

However, these anti-adhesion material is a sheet material, for it is difficult to, for example, three-dimensional shape or the cylinder shape of the organ, in vivo or in complex shapes such as medical apparatus. Furthermore, if the above-mentioned "Seprafilm" as such as, if wetting is difficult in operability, there are also problems in operation. Furthermore, in recent years, increasing use an endoscope, a laparoscope in operation, the operability of the anti-adhesion material of the sheet becomes more difficult, that is substantially unable to use the.

Therefore, in order to improve the convenience of application, in order to form part of the supply, and in the application and by the temperature changes in the shape, changes in nature, and the like, become such as solid, so as to protect, separation, reinforcement, the material of the buffer effect, or on the contrary in order to solvate the supply, and in the application of the stimulation by the effect of changes in the material of the liquid thus play attention in recent years. For example, has been the use of temperature-responsive high-molecular endoscopic or laparoscopic surgery has fluidity at room temperature in the form of the liquid supplied to the body, and the part attached to the body temperature of the solid material and the barrier properties of, and studied as a trauma or surgical material coated with the anti-adhesion material, adhesive to use (for example, Patent document 1).

Such attention as the stimulus responsive polymer, such as are known to the temperature-responsive polymer. Temperature-responsive high-molecular material has the following generally known: the display is in a hydrated state of the above high molecular at some temperature or volume to form the hydrate, the nature of the lower limit of the variation of the critical temperature of the solution (Lower   Critical   Solution   Temperature; the following abbreviated as LCST) of those, and display at some temperature by more than the volume or shape of hydration, such as the upper limit of the change in the nature of the critical temperature of the solution (Upper   Critical   Solution   Temperature; the following abbreviated as UCST) of those. As the display of those UCST, such as are known to N-acetyl acrylamide and acrylic amide copolymer (for example, Patent document 2); those of the LCST as a display, for example, are known to N-isopropyl acrylamide (NIPAM) homopolymer or copolymer of (for example, Patent literature 3), or Poloxamer, and the like. Especially poly N-isopropyl acrylamide (PNIPAM) in proximity to the temperature of the is compound 32 the swelling-shrinking near [...] the volume of the transfer to form a solid gel, as represented in the medical material, carried out extensive research (for example, Patent document 4).

However, they have such a stimulus responsive polymer while it is true that the excellent convenience, but normally solid (gel) elastic, low strength and the like, so that the use of the mechanical characteristics required by the problem of insufficient. For example, as an anti-adhesive material with the problem of insufficient barrier property. Furthermore, for example in the medical field, usually known that if the implant in the machine body organ with different mechanical characteristics of the artificial material, will be occurring in the organism due to the mechanical properties of the body caused by the different reaction, the visceral organ in the machine body with the same high mechanical characteristics by the demand of the material. Furthermore, when the as the actuator, the gel need to be able to fully tolerized is applied to the actuator of the resistance of the mechanical strength.

Therefore, in order to improve the mechanical characteristic of the various novel high molecular research. For example, the temperature of the gelling takes place a response which is poly (ethylene glycol-block-(DL-lactic acid-random-glycolic acid)-block-glycol);   (PEG-PLGA-PEG) triblock copolymer, or (PLGA-PEG-PLGA) triblock copolymer (for example, Patent document 5). And then, the branched polyether and polyester block copolymer branch of research has been conducted (for example, Patent document 6).

However, if the introduced into the high molecular material used for improving the mechanical properties of the temperature-responsive group functional group will be reduced relatively, thus unable to stimulate the response function with the height of, or to the mechanical characteristics and corresponding to the requirements of the various uses the characteristic (for example, biodegradable, biocompatible, low toxicity,).

So, the status quo is not obtained the convenience and excellent mechanical characteristics is the stimulus responsive material.

Literature of the prior art

Patent literature

Patent literature 1: Japanese opens especially 2003-252936, the

Patent document 2: Japanese opens especially 2000-86729, the

Patent literature 3: Japanese extra Kaiping 11-228850, the

Patent literature 4: Japan opens especially 2004-307523, the

Patent literature 5: Japan opens especially 2012-12606, the

Patent literature 6: Japan opens especially 2009-29967 of communiques.

Content of the invention

Problem to be solved by the invention

For the above-mentioned problem, as long as it can find the stimulus responsive polymer mechanical characteristics, with the convenience and high mechanical characteristics is, so as to solve the above-mentioned problem. For example, in the coating or adhesive, sealing material and other general materials, coating material or trauma, such as anti-adhesion material of the medical material of the film, in use, with the transport or can be easily supplied to the convenience of the material to a suitable position, and firm complex , the operability and the effect is remarkably improved. Concretely, for example, the material in order to liquid supply, and in the application of the part can be firmly and stimulating to the material of the coating. In particular the anti-adhesion material, the use of sheet material of the anti-adhesion material because of the complicated shape, the gleyness, the operability, such as an endoscopic or laparoscopic surgery supplies to the affected part, such as in the application of a problem, thus expect solve the above-mentioned problem of the anti-adhesion material.

The subject of this invention is to provide which combines the convenience and mechanical properties of the stimulus responsive material and medical material using the same.

For the method of solving the problem

In view of the above problems, the invention has the following composition. In other words, the invention relates to a display stimulus responsive to the stimulus responsive material, which comprises a stimulus responsive polymer, fiber and water, the number of the average diameter of fiber 1-900nm, and the presence of the fiber dispersion. Furthermore, the medical material of the present invention using the stimulus responsive material of the present invention.

The effect of this invention

According to the present invention, can provide both convenience and high mechanical characteristics is the stimulus responsive material. Or, as other views of the invention of the application, according to the present invention, can improve the many kinds of stimulus-responsive high polymer mechanical properties.

Mode of execution

The invention said stimulus responsive means lightfield irradiation, electric field is applied, temperature (heat) change, pH change, and adding chemical substances stimulate a response, with the stimulation and the stimulation before and after the nature of the shape and/or the nature of the variation, such as, for example, expansion and contraction of the volume change, the change of the liquid and solid shape (sol-gel transfer), the solution to the dispersion of the shape change of the variation of the. In particular, the change of the liquid and solid shape (sol-gel transfer) before and after the stimulation of the change in the mechanical characteristics of the response is more prominent, the preferred forms of the invention. As the stimulus responsive, in particular stimulating response to the latter method of determining the difference of the storage elastic modulus is preferably 10 Pa or more, more preferably 100 Pa or more, further preferably 1000 Pa or more.

Embodiments of the invention in the stimulus responsive material, through stimulus responsive polymer of the fiber, such as mutual role, the stimulus responsive polymer of separate strength, elastic modulus, viscosity, shape stability of the effect of mechanical properties. Embodiments of the present invention the stimulus responsive material must have stimulus responsive, as described below, according to the stimulus-responsive high polymer or fiber concentration, ratio, chemical structure, shape and the like play a stimulus responsive. The invention said stimulus responsive polymer is appropriate to set the concentration of the, condition and display stimulus responsive polymer. Stimulus responsive polymer will occur in stimulation response back and forth, such as shape and/or the nature of the change, to the mechanical characteristics of the fibers also can be changed to improve the effect. For example, stimulus responsive polymer to water with respect to the lower limit of the temperature of the critical solution temperature (LCST) of the responsive high-molecular, can also play the following specific effect: below the critical temperature of the flow properties of the state of the mechanical characteristics (sol) and maintaining the fluidity improving effect is small, but if it reaches a critical temperature above which greatly improve the mechanical characteristics. Furthermore, embodiments of the present invention the medical material, in particular to anti-adhesive material has stimulus responsive, to stimulate the front and back, and/or the nature of the shape changes such as, for example, this can be realized by the following effect: when the fluidity is maintained supplied to the affected part, and the loss of flow properties of the attached as the function of the anti-adhesion material.

Embodiments of the present invention the stimulus responsive material stimulus responsive material is preferably a 25 the under [...] the storage elastic modulus is less than 100 Pa. Through is less than 100 Pa, even if it is a pipe, or the shape of the mouth with a horn (splay), and the like of the machine, can be easily supplied to the using site, or otherwise easily discharged. Therefore, more preferably 50 Pa the following. Furthermore, the film effect from further play or anti-adhesion effect the point of view of a variety of effects, the 30-60 [...] , preferably 30-45 the under [...] the maximum storage elastic modulus is 100 Pa or more is preferred. More preferably 300 Pa or more, further preferably 1000 Pa or more. At this moment there is no particular limitation to the upper limit of the, usually to 50000 Pa the following.

The invention the maximum storage elastic modulus refers to the determination of storage elastic modulus in the range of the maximum of. In the invention, the storage elastic modulus (G')using the sample liquid is to be measured into by board interval of 1 mm is provided with a parallel plate in the device for measuring the dynamic viscoelasticity, and 5 minutes later, in the stress 4dyne/cm², heating speed the 0.5 [...] /min, angular velocity 1rad/s obtained under the value of the measured. For measuring temperature, the temperature-responsive polymer in the situation the 25-60 [...] , the temperature-responsive high-molecular materials other than the, will stimulate the temperature measurement is set in front of the 25 [...] , in the stimulation at the same time the 30-60 [...] determine under the temperature range.

As in the embodiment of this invention the stimulus responsive material is preferably used in the stimulus responsive polymer, for example, as the temperature-responsive high-molecular, can cite poly (N-isopropyl acrylamide), poly (N-isopropyl acrylamide-acrylic acid) copolymer, poly (N-isopropyl acrylamide-methacrylate) copolymers, poly (N-isopropyl acrylamide-sodium acrylate) copolymer, poly (N-isopropyl acrylamide-vinyl ferrocene) copolymer, poly (vinyl methyl ether), poly N-substituted acrylamide derivative or poly N-substituted methyl acrylamide derivatives, the hyaluronic acid is copolymerized with temperature-responsive high-molecular hyaluronic acid derivative, poly amino acid derivatives, polyester peptide (polydepsipeptide), by the α / β-asparagine derivatives synthetic poly asparagine derivatives, poly epoxy propane, propylene oxide with other alkylene oxide copolymer, polyvinyl methyl ether, polyvinyl alcohol part acetyl compound, such as polyalkylene oxide, or poly (ethylene glycol-block-(L-lactic acid)); (PEG-PLLA) diblock copolymer, poly (ethylene glycol-block-(D-lactic acid)); (PEG-PDLA) diblock copolymer, poly (ethylene glycol-block-(DL-lactic acid)); (PEG-PDLLA) diblock copolymer, triblock copolymer (PEG-PLLA-PEG), triblock copolymer (PEG-PDLA-PEG), (PEG-PDLLA-PEG) triblock copolymer, poly (ethylene glycol-block-DL-lactic acid-random-glycolic acid-block-glycol); (PEG-PLGA-PEG) triblock copolymer, triblock copolymer (PLLA-PEG-PLLA), (PDLA-PEG-PDLA) triblock copolymer, triblock copolymer (PDLLA-PEG-PDLLA), (PLGA-PEG-PLGA) triblock copolymer, comprising a branched structure of the polylactic acid PEG (branch PEG-PLLA) block copolymer, (branch PEG-PDLA) block copolymer, (branch PEG-PDLLA) block copolymer, (branch PEG-PLGA) block copolymer, copolymers of lactide and polysaccharides, polyether and polyester copolymer and its derivatives, and the like, polyester and polyether block copolymer prepared by copolymerizing, hydroxy alkyl chitosan, the hydroxy acid unit and aspartic acid unit into the polyether chain of the copolymer, or their derivatives or cross-linked high molecule and the like. Furthermore, also can be the methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose or other alkyl-substituted cellulose derivatives, etc., cellulose and with other temperature-responsive high-molecular composition by copolymerizing in the cellulose derivatives, into the high molecular weight type material or substituted base and so on , therefore the display temperature-responsive, thus is used for the invention. For example, although the simple Carboxymethylcellulose there are also non-display temperature response improved, but carboxymethyl cellulose, methyl cellulose and polyalkylene oxide and the like may be copolymerized is a derivative of the temperature responsive, is the preferred mode.

Furthermore, the chemical substance is added, and the like as being response of the high-molecular, electrolyte or ionic substance can be used with strong ionic polymer combined, for example, the polyvinyl sulfonic acid can be cited of crosslinked material or its derivative or the like the combination of the cationic surface active agent. Furthermore, reference may also be made, having the disulfide cross-linked cellulose acetate by means of oxidation and reduction can be carried out reversibly examples of sol-gel transition.

As a humidity-responsive high-molecular, cellulose acetate, for example, can be cited.

As a light-responsive high-molecular, can be cited such as: the adoption of containing diazo compounds such as cis-trans transition light of the high molecular compound, through the ultraviolet and gelation of the carboxymethyl cellulose into high molecular photoreactive group, through radiation and gelation of carboxymethyl cellulose and the like.

As a pH-responsive polymer, such as electrolyte system can be used with alkaline group high-molecular or high-molecular compound. As a specific example, can be cited: polyacrylic acid metal salt or its derivative and cross, polyacrylamide derivatives, crosslinked object poly alkyl sulfonic acid or its derivatives and metal salts, metal salts of carboxy alkyl cellulose, such as a crosslinked object.

Embodiments of the invention in the stimulus responsive material, is not limited to the above-mentioned, various kinds of stimulus responsive polymer can use 1 kind of, or the 2 combination of the above. Because chemical cross-linking reaction caused by the irreversible display the stimulus responsive polymer due to the side reaction of the residual reaction product or not, depends on the use of the results of the sometimes display less preferred, since the physical cross-linking and the like and the display reversibilities the stimulus responsive polymer as a result of this concern, and preferably less.

Stimulus responsive polymer in the above, from the point of view of the medical material, preferably the temperature-responsive polymer. As the temperature-responsive high-molecular, for example, can be cited, the UCST or LCST the 0-80 [...] responsive to the temperature of the high-molecular, but is not limited to this. From suitable for the preferred embodiment of this invention use the stimulus responsive the point of view of the use of material, stimulus responsive polymer is preferably having responsive to the temperature of the LCST polymer. Here, the critical temperature of the solution is directed form and/or nature of change threshold temperature, hydrated with the to as the transition temperature of the hydrate, with the temperature of the LCST in responsive high polymer, have the following properties: the LCST following is the state of having fluidity (sol), more than the LCST (gel) is solid state. From the room temperature to the vicinity of the point of view of the operation of the, preferably critical solution temperature is 0-80 the those [...] , more preferably critical solution temperature is 20-70 the those [...]. Furthermore, as the external stimulus is adapted to the temperature of a medical material, in particular, can easily embody the viewpoint of anti-adhesion effect, further preferably critical solution temperature is 20-50 the those [...]. As a specific example, such as the above-mentioned temperature-responsive high polymer shown in the example, wherein the embodiment of the present invention as the stimulus responsive material of the anti-adhesion material, is biodegradable, the liquid material at room temperature, for in vivo are solid gelationus body, as a result of the operation is easy, and preferably.

Preferably adjusted corresponding to the specific use for the critical temperature of the solution, for example, if the copolymerization of hydrophobic polymer or monomer, the critical temperature of the solution can be reduced, if copolymerized hydrophilic polymer or monomer the critical solution temperature can be raised. For example, as a hydrophilic high molecular compound, can cite: polyethylene oxide, polyvinyl alcohol, poly N-vinyl pyrrolidone, and the like. Should be note, stimulus responsive material, although it has been the critical temperature of the stimulus responsive polymer of the impact of the critical temperature, sometimes a stimulus responsive polymer separate slightly different, thus preferably suitable for adjustment.

These stimulus responsive polymer molecular weight there is no particular limitation, the fiber from the viewpoint of dispersibility, preferably contains a number average molecular weight of 3000 or more stimulus responsive polymer, more preferably containing at least 1 million or more stimulus responsive polymer.

From play can be significantly more stimulating response of the shape and/or the nature of the point of view of changes, stimulus responsive polymer relative to the stimulus responsive of the weight of materials that the concentration is preferably 50 wt % or less, more preferably 30 wt % or less, further preferably 20 wt % the following. Furthermore, from improving the mechanical characteristics of the stimulus responsive material point of view, is preferably 0.10 wt % or more, more preferably 0.50 wt % or more, further preferably 1.0 wt % or more.

Embodiments of the present invention the stimulus responsive material fiber is used in the cellulose, chitin, chitosan, rayon, acetate, natural fiber or regenerated fiber, anti-synthetic fiber, polyamide or polyester, polyolefin or other synthetic fiber or the like, and no particular limitation, but the stability of the quality, the uniformity of the diameter of fibers, the easiness of manufacturing extremely fine fibers, high intensity or the degree of freedom of design, low cost, safety, perspective, preferably synthetic fiber. For example, the cellulose fiber the beating can be extremely fine fibrils cellulose nano-fiber, the diameter of the fiber, however, is not uniform and the tendency of uneven performance. Furthermore, as a synthetic fiber of high-molecular, can be instantiated: polyester or polyamide, polyolefin, polyphenylene sulfide, phenol resin or polyacrylonitrile, polyvinyl alcohol, polysulfone, fluorine-based high molecular material or their derivatives, and the like, and no particular limitation.

As a polyester, can be cited: polyethylene terephthalate, polyethylene glycol 1, 3-propylene glycol ester, polybutylene terephthalate, polylactic acid, polyglycolic acid, or its copolymer. Furthermore, as a polyamide, can be cited: nylon 4, nylon 6, nylon 66, nylon 11, or its copolymer. As the polyolefin, can cite: polyethylene, polypropylene, polystyrene, or its copolymer. Fiber can contain particles, flame retardant, antistatic agent and other compounding agent.

Among them, from the viewpoint of dispersibility is good fiber, particularly preferred JIS L 1030-2 (2005) of the official moisture in the 0.5 the above fiber. For example, the preferred mode is the nylon as a 4.5, acrylic is 2.0, polylactic acid as a 0.5. On the other hand, polypropylene or carbon fiber as the 0.0, from the viewpoint of dispersibility is not preferably, less than 0.5 in the case of the fiber, the fiber surface, preferably by oxidation of, for example, grafting, or copolymerization of hydrophilic ingredient blend to modification. Of course, such as from the point of view of improving dispersibility, also preferably to 0.5 or more modifying the fiber.

Furthermore, embodiments of the present invention the stimulus responsive material of the fiber through the number of the diameter of the monofilament can, on average (number average diameter) to 1-900nm. Preferably 700 nm the following, more preferably 500 nm or less, further preferably 200 nm the following. The 900 nm the following, to improve the dispersibility of the fibers, and the fiber with the stimulus responsive high-molecular interaction becomes more prominent, high mechanical characteristics of the play to improve the effect. For example, the use of the clothes and generally used in commercial fiber size (0.5-5dtex, nylon 6 (density 1.14) of the case, a diameter of about 7.5-23.6 the  m), fiber more has the mechanical characteristic of the tendency of the reduced direction. On the other hand, there is no particular limitation to the lower limit of the diameter, the operability is excellent, however, play a mechanical properties to the point of view of effect, is preferably 1 nm or more.

There is no particular limitation to the fiber length, from the fiber of the point of view of good dispersibility, preferably 10.0 mm the following, further preferably 5.0 mm the following. Furthermore, the operability or stimulus responsive material from the perspective of improving the mechanical characteristics, is preferably 0.01 mm or more, more preferably 0.1 mm or more. Furthermore, excellent mechanical properties from the point of view of effect, preferably the value of the length obtained by dividing the (L/D) diameter of 200 or more, more preferably 1000 or more. On the contrary, from the viewpoint of excellent dispersibility, preferably L/D to 100000 the following, more preferably 10000 the following.

In this text, the number of the invention the average diameter of fibers and the fiber length is the value obtained by the following method. First of all, the sample is, in the 60 the drying [...] , with the scanning type electron microscope (SEM) or an optical microscope observation, stochastically determining 30 of the diameter of the fibers, the fiber length. The sampling and observation is repeated 10 times, the total 300 of the diameter of the fibers, the fiber length to its simple average of the data of the value of the obtained. Should be note, the length of the fiber, the fiber length is 5.0 mm when the above, by JIS L 1015 (2010) determines 8.4.1C method.

Synthetic fiber manufacturing method without particular limitation, for example, in addition to outside the direct spinning process, can also be composed of sea-island type composite spinning or blend, alloy, composite spinning method, and the like. Furthermore, also can be solution spinning, melt spinning, any method for electrostatic spinning, and the like, is not particularly limited. Wherein low cost and from the point of view of uniformity of the diameter of the, preferably sea-island type composite melt spinning method.

Furthermore, the cellulose fiber, there is no particular limitation to use can be derived from plant (such as wood, cotton, bamboo, hemp, jute, kenaf, agricultural waste), animal (such as ascidia class), algae, microorganisms and the like (for example, acetic acid bacteria (Acetobacter)) the cellulose fiber or the like. From the viewpoint of obtain an easy, preferably plant-derived cellulose fiber. Cellulose fiber can be used for the refinement by well known to those, can be cited such as:by using a refiner or high-pressure homogenizer, a medium stirring mill, stone mortar, grinder, water jet to carry out grinding or the beating so as to fibrillate or microfined method, by acid hydrolysis or the chemical treatment, such as refining method, the microorganism producing method, in order to wet dissociates after the role of the enzyme at the same time through the use of the cooking treatment, physical treatment of a method of fine fibrosis to manufacture, or by electrostatic spinning method as regenerated cellulose fiber or method, and the like of the refined cellulosic fiber.

Chitin fiber can be through from biological extraction method, or by the synthetic or semi-synthetic fiber is a high molecule is manufactured. The shell of the crustaceans of crab or shrimp and the like contained in a large amount such as chitin fiber monofilament diameter is 10-20nm left and right, also has a fiber length of several mm of the longer fiber length, obtained from the point of view of high mechanical characteristics, which can be preferably used. Extracting the shell from a crustacean chitin fiber method, for example, can be through the mill shell of the crustaceans of pulverize and with an alkali, fully mixing, washing, then mixed and fully stirred with an acid, washing method, or the commercial refined chitin powder grinder for adding acetic acid and well known method such as method to manufacturing.

Embodiments of the present invention the stimulus responsive material fiber in water or stimulus responsive polymer, or water and stimulus responsive polymer are dispersed in the complex. By this, through the stimulus responsive high-molecular interaction, can make the mechanical characteristic is improved, or the stimulation response before and after the change in shape or nature. The dispersion of the invention is means, such as non-woven fabric or paper, such as sponge, such as interweaving or bonded fiber because not form the state of the independent structure, therefore, comprises a stimulus responsive polymer, fiber and water material may be before or after the empowerment of stimulation are display mobility. The dispersion morphology, dispersion stability or from the point of view of mechanical characteristics, is preferably mainly to the state of the dispersion of fibers, can also be a fiber bundle, the fiber aggregate (for example 100 the following   m) dispersed in a state, can also contain in one part.

Evaluation of dispersibility of the fibers are not particularly limited, for example, the stimulus responsive material can be any position of the optical microscope or microscope for observation, the Image is divided into the block and the count number of the fibers, of the fiber through the block to the deviation of the number of the evaluation of dispersibility.

From play can be significantly more stimulating response of the shape and/or the nature of the point of view of changes, the concentration of the weight of the fiber is preferably 10 wt % or less, more preferably 5.0 wt % or less, further preferably 3.0 wt % the following. Furthermore, from improving the mechanical characteristics of the stimulus responsive material point of view, is preferably 0.01 wt % or more, more preferably 0.10 wt % or more, further preferably 0.50 wt % or more.

Embodiments of the present invention the stimulus responsive material of the stimulus responsive high-molecular weight ratio of the fiber (stimulus responsive polymer/fiber) is preferably 5-100. The ratio is the weight of 100 the following, can make the fiber relative to the stimulus responsive polymer moderately dispersed, so that the mechanical characteristic is improved. Furthermore, through making the weight ratio of 5 or more, the mechanical characteristics of the fiber by improving the effect becomes remarkable. Weight ratio more preferably 7-50, further preferably 10-30. Furthermore, the weight ratio of 1 when it is under, each other due to the fiber winding or stimulus responsive high-molecular contribution to the reduction, comprising a stimulus responsive polymer, the material of the fiber and water sometimes did not display stimulus responsive.

As a method of dispersing the fibers, can be made by using a high speed mixer, Henschel mixer, a super mixer, homogenizer, etc. the physical mixing method of disperse, or by using ultrasonic dispersion machine and the like of the ultrasonic vibration caused by dispersion method, such as the known method. Furthermore, if the dispersed fiber in advance in the surfactant is added to improve the dispersibility of the fiber, so preferred.

The invention the basic chemical structure in the stimulus responsive polymer or fiber in a single or a plurality of can be present. A basic chemical structure is that of high molecular to form a unit, for example, if it is poly-lactic acid means that the lactic acid unit (-O-CH (CH₃)-CO-), if it is polypropylene the propylene unit (-CH₂-CH (CH₃)-), if it is a polyethylene terephthalate means that terephthalic acid and ethylene glycol unit (-O-CO-C₆ H₆-CO-O-CH₂ CH₂-) or ethylene glycol unit (-CH₂ CH₂-O-), if it is 6 nylon is refers to the nylon 6 unit (-CH₂ CH₂ CH₂ CH₂ CH₂-CO-NH-) or amide unit (-CO-NH-), if it is the polyethylene glycol is ethylene glycol unit to (-CH₂ CH₂-O-), if it is poly (N-isopropyl acrylamide) means that N-isopropyl acrylamide unit (-CH₂ CH (CO-NH-CH (CH₃)₂)-) or amide unit (-CO-NH-), if it is the cellulose the glucose unit, if it is the chitin the glucossamine unit or amide unit such as (-CO-NH-) a unit. Preferably a unit of the main chain, but can also be introduced by chemical modification of the side chain of the main chain.

Solubility parameter (SP value) is the solubility of the expressed material or hydrophilic? The parameter of the inherent hydrophobic substance. The SP value of the present invention by the Fedors method [Fedors, R. , Polymer Eng. Sci. , 14, 147 (1974)] determined. Fedors that in the method, the value SP the cohesive energy density with a molar volume depending on both the type and quantity of the substituent, can be through the numerical expression (1) to calculate.

The numerical expression (1)

[D 1]

(Here, ΣE_coh said cohesive can, said ΣV molar volume).

Basic chemical structure is composed of 2 or more of the segments, such as the numerical expression (2) as shown, the basic chemical structure of the number average molecular weight to the number average molecular weight of the molecule as a whole of the fraction multiplied by the solubility parameter of the basic chemical structure, as the SP value of the sum.

The numerical expression (2)

[Few 2]

(Here, in the formula δ said solubility parameter, Mn_k said the basic chemical structure of the number average molecular weight, Mn expressed molecule the overall number average molecular weight of, δ_k said the basic chemical structure of the solubility parameter).

Furthermore, basic chemical structure includes 2 a plurality of the above, to use specific at least 1 kind of the basic chemical structure of the SP value, but can also be if numerical expression (3) as shown, the basic chemical structure of the number average molecular weight of the fraction multiplied by the SP value of the basic chemical structure, and to the embodiment of the invention as the sum of the SP value of the stimulus responsive material.

The numerical expression (3)

[Few 3]

(Here, in the formula δ said solubility parameter, Mn_k said the basic chemical structure of the number average molecular weight, Mn indicated that a number average molecular weight of, δ_k said the basic chemical structure of the solubility parameter).

Stimulus responsive polymer in basic chemical structure of the SP value of at least 1 kind of, and the fiber in basic chemical structure of the SP value of at least 1 if the value of the SP 0-10, the stimulus responsive polymer can be obtained the interaction of the fiber becomes large, or the effect of improving the dispersibility of the fibers, so preferred. More preferred is the difference between the SP 0-5, further preferably 0-1.5. Should be note, such as the amido (-NH-CO-), for example, in (-NH-CO-) unit in the case, and into (-NH-) unit and (-CO-) unit in the case, the calculated value of sometimes produce different, in this case preferably at least 1 kind of result of calculation in the case of fall into the above-mentioned range in the difference between the SP. The SP value is the decimal section 2 bit-rounding find, are respectively the difference between the SP to the stimulus responsive polymer and the textile fiber asks value SP, and the absolute value of the difference.

The embodiment of the invention in the stimulus responsive material, the interaction of the fiber from the point of view of strong, stimulus responsive polymer and the fiber preferably has a common basic chemical structure. Basic chemical structure is more preferably in a part of the containing amide unit in, hydroxy acid unit, glucose unit, mechanical characteristics from the point of view of improving the effect remarkable, further preferably contain amide unit, and from a biodegradable is the point of view of the medical material, further preferably contain aliphatic hydroxy carboxylic acid unit. As the aliphatic hydroxy carboxylic acid unit, can be cited such as: lactic acid unit (-O-CH (CH₃)-CO-), glycolic acid unit (-O-CH₂-CO-), glycerin acid unit (-O-CH₂-CH (OH)-CH₂-), hydroxy butyric acid unit (-O-CH (CH₃)-CH₂-CO-), malic acid unit (-O-CH (COOH)-CH₂-CO-), and the like, there is no particular limitation, can alone or 2 or more mixed for use. In having an asymmetric carbon atom in the case of the optical isomer of the compound, can be used any thereof. In particular, poly N-substituted acrylamide derivatives, poly N-substituted methyl acrylamide derivatives, in particular is PNIPAM stimulus responsive polymer, and nylon and the like polyamide fiber or chitin fiber combination of a common amide bond by realizing excellent mechanical characteristic improving the effect, is the preferred mode. Furthermore, if it is has a hydroxy carboxylic acid unit, in particular of lactic acid unit stimulus responsive polymer and the fiber (poly lactic acid fiber or polyglycolic acid fibers, or the like) of the combined, can be with biodegradable and high mechanical characteristics, can be prepared into suitable for use of the medical material, in particular the material of the anti-adhesion material use. Before chitin of a biodegradable fiber, can be prepared into suitable for a material of the medical material. Polylactic acid can be through 2 molecule by dehydrating condensation of a hydroxy carboxylic acid of the c cyclic di-ester to obtain the ring-opening polymerization, the body L lactide lactide, lactide body third D, lactide racemate DL, can be used with other monomers lactide copolymer or multi-block copolymer, graft copolymer or the like.

The fiber of the stimulus responsive polymer to improve the effect on the mechanical characteristic, as noted above, stimulus responsive polymer of the fiber the smaller the difference between the SP, or have a common basic chemical structure, the greater the surface free energy, fiber length/fiber diameter (L/D) okoshi large, the effect of the tendency of the more becomes larger.

The embodiment of the invention of the stimulus responsive material comprises a stimulus responsive polymer and fiber, and water. Stimulus responsive polymer in stimulating response state of at least either the front and rear of the, preferably dispersed and/or dissolved in water.

Furthermore, in order to make the stimulus responsive polymer or fiber is dispersed or dissolved in water, preferably containing surface-active agent. As the surface active agent, preferably an anionic or non-ionic system. And then, also can be added according to the needs of various preservatives, dispersion stabilizer, electrolyte, and the like. By containing surface active agent, also can be expected to improve the effect of the mechanical characteristic. The greater the molecular weight of the surfactant by adsorption is the more active the surface of the fiber for each other to make the stereoscopic exclusion effect of improving dispersibility, therefore, preferably, the number average molecular weight of the surface active agent is preferably 10000-100000, more preferably 30000-100000. Furthermore, preferably the surfactant concentration relative to the fiber containing 1-500wt %, more preferably contain 10-300wt %.

The embodiment of the invention of the stimulus responsive material may be a reversible or the irreversible. By containing fiber, the moisture from the stimulus responsive material evaporation can also maintain the shape.

The embodiment of the invention because the stimulus responsive material having high mechanical characteristics, which is especially suitable for coating material. Incasemented of the present invention as long as it is covered for the use of object positions or bonding, sealing, there is no particular limitation, can be in order to, for example, the film material, sealing material, adhesive material, to-use of the medical material. In particular, can be preferably used for, for example, wound coating material, anti-adhesion materials, surgical adhesives, sealing material, such as material for medical use, foundation, volley medicinal preparation cosmetics such as, adhesive, coating material, paint and other industrial products. Wherein liquid from the to supply to the affected part, and having high mechanical characteristics to the point of view of the solid, used for medical material is particularly useful mode. In the medical material, the anti-adhesion material, in addition to the ease of application of the complex shape of the outside part, from the can in laparotomy or laparoscopic, endoscopic surgery during the surgical operation, such as play a suitable convenience the viewpoint of excellent effect of, in a manner which is particularly preferred.

Embodiment

Embodiment the processed matter measured through the following method.

A. High molecular melt viscosity

Capilograph through dongyang of the stool   1B detecting high molecular melt viscosity. Should be note, starts from the sample inputs of a high molecular retention time is set to 10 minutes.

B. Melting point

Perkin     DSC-7     Elmaer use, to 2nd     run displaying high-molecule in the melting of high temperature as that of the peak of the melting point of the molecule. The temperature rising speed at this moment is the 16 [...] /minutes, a sample size of 10 mg.

C. Cross-sectional observation

(TEM) through a transmission type electron microscope (Hitachi society system H-7100FA-type), the direction along the cross section of the fiber to observe ultrathin section cut. Nylon with phosphotungstic acid metal dyeing.

D. Fiber to observe the state of the

A sample of the fiber dispersion, is placed in the glass plate, through microscope ([...] (strain) systems) to 200 times observed.

E. Number average diameter of fiber

In the sample 60 the after drying [...] , carry out SEM observation, measuring fiber diameter, the simple average of the obtained. At this moment, is used for determining the average determination number 5 mm square of random in the sample 30 of the diameter of the fibers, and then carry on the 10 samples, access to all 30 the diameter of one single filament textile fiber data, from the total 300 the diameter of the root of the determined average data. Special-shaped cross-section of the fiber in the case of, first measuring the sectional area of the fibers, will be assumed that the area is the area of the cross section is round. The number calculated by the area of the obtained average diameter of the fibers. Here, the fiber diameter is in units of nm, measured from 300 to the diameter of the fibers of the article after decimal point 1 bit, and comparing the average value of the section 1 is rounded.

F. Fiber length

By JIS L 1015 (2010) determines 8.4.1C method. The measurement result is less than 5.0 mm are, by using a value obtained by the following method.

In the sample 60 the after drying [...] , through SEM observation or optical microscope measuring fiber length, the simple average of the obtained. At this moment, is used for determining the average of the random determination number 30 root of fiber length, and then carry on the 10 samples, all 30 of the data of the single-fiber fiber diameter, the total 300 fiber length of the simple average of the determined data. Flexing of the fiber as far as possible to be measured. Here, the fiber length is in units of mm, measuring from 300 fiber length of the fibers after the decimal point of the section 2 is arranged, and rounded to 1 bit.

G. Storage elastic modulus (G')

Viscoelastic of determining and using system rheometer Anton Paar " Physica MCR301 the to [...] (registered trademark). The assay conditions are as follows.

? Plate: parallel plate (φ 25 mm)

? Plate interval: 1 mm

? Stress: 4dyne/cm²

? Angular frequency: 1rad/s.

H. Fiber dispersion evaluation

A sample of the fiber dispersion, is placed in the glass plate, through microscope ([...] (strain) systems) to 20 times observed.

The calculation of I.SP

Basic chemical structure of the solubility parameter is the method of using the Fedors, its unit to (J/cm³) 1/2 calculate, the decimal section 2 is rounded to decimal section 1 is obtained and. The difference between the SP are respectively find the stimulus responsive polymer of the fiber after the SP value, the absolute value of the calculated difference.

J. Anti-adhesion effect

After anesthesia of the RAT with pentobarbital sodium, the abdomen-cut and make the ceca exposed. The ceca surface of wiping the wiping paper, after drying, will contain 40% ethanol aqueous solution to the filter paper (1 cm × 1 cm) attached to the exposed on the caecum, placing 5 minutes. After removing filter paper, will stick to paper opposite the part of the of serosa (5 mm × 5 mm) injury. The cut part of the muscle layer and skin suture, the suture portion disinfection of povidone-iodine. Breeding 2 months later, disembowelment formed when equivalent to the following scoring 3 adhesion.

The adhesion score observed by naked eye

Rating 0: not recognizing that the adhesion state of the

Rating 1: has a kneading weak adhesion the musclar layer of separation degree of the state of the

Score 2: has the appendix can be stripped and musclar layer adhesion degree the state of the degree of

Rating 3: and musclar layer with the difficulty of stripping of the state of the adhesion of the appendix

Using the above-mentioned model to evaluate the anti-adhesion effect. The 1 ml composition sending 2.5 ml in of the injector, the aqueous solution containing ethanol is attached to a part of the filter paper, through 20 knitted   G composition of coating in the injector. In 2 months after the moment paunching, for arbitrary composition, in the abdominal cavity are not visible to the naked eye of the residual fragment. To 2 months after the evaluation of the adhesion effect.

<test example 1>

Embodiment 1

The melt viscosity 500 Pa? S (the 262 [...] , the cutting speed 121.6 sec^-1), melting point 220 the [...] nylon 6 (N6) (50 wt %), and 8mol % melt viscosity 310 Pa? S (the 262 [...] , the cutting speed 121.6 sec^-1), melting point 225 the [...] of isophthalic acid and 4mol % bisphenol of the melting point of the copolymerized A the 225 [...] the copolymerized terephthalate (PET) (80 wt %)using two-axis extrusion mixer in 260 the mixing [...] , get b^* value = 4 polymer alloy chip. Should be note, the copolymerization of PET 262     , 1216 sec^-1 the melt viscosity under 180 Pa? S. The polymer alloy melt after filtering, the temperature of the surface of nozzle 262 the melt spinning under [...] , get 120dtex -12 the fibrous composite fiber. The resulting high molecular alloy TEM the cross section of the fiber is used for observation, the results display N6 an island component (circular portion), copolymerized PET (other part) to sea island component structure.

The resulting composite fiber aqueous sodium hydroxide solution for removing the sea component, with the guillotine type cutting machine cut into the fiber length is 1.00 mm. By the observation of the cross section of the fibers, the number of the results of the average diameter of the single strand of 120 nm.

Furthermore, the resulting fiber and water in the beater to the beating in Niagara, PFI mill and further the beating, be 10 wt % of a mixture of fibers with water. And then, join the mixture 5.5g and a nonionic surfactant (polyoxyethylene styrene sulfonation ether , a number average molecular weight of 1 million) and water, into the beater, the fiber dispersed in water.

In the thus obtained fiber dispersion in adding poly N-isopropyl acrylamide (PNIPAM) ([...] (strain) systems, molecular weight 2-2.5 million), the stimulus responsive material. Stimulus responsive material at this moment the weight concentration is 1.0 wt %, the average number of short fiber diameter is 120 nm, L/D to 8333, weight of surface active agent concentration is 1.0 wt %, PNIPAM the weight concentration of the 10 wt %.

The resulting stimulus responsive material in the 25 has fluidity [...] , storage modulus of elasticity of 20 Pa. In some, the heating if the 35 [...] form a solid gel. Furthermore, heating to instillment in 40 the standard agar culture medium [...] , and observe the shape change, the result does not display mobility to be transformed into a solid gel. 30-60 the under [...] the maximum storage elastic modulus at about 37 the display is under [...] 10789 Pa. The results recorded in table 1.

Should be note, N6 of the SP value (-(CH₂)₆-CONH-) unit calculates the 25.4, PNIPAM of the SP value (-CH₂-CH-CONH-CH (CH₃)₂-) unit calculates the 24.6, SP the value 0.8.

Embodiment 2

The concentration changing weight PNIPAM and replaced by adding methyl cellulose (MC) (Shin-Etsu chemical (strain) systems "   SM4000 the Metolose [...]), in addition to the embodiment 1 of the same. The fiber of the composite material of the weight concentration is 1.0 wt %, the average number of short fiber diameter is 120 nm, L/D to 8333, weight of surface active agent concentration is 1.0 wt %, MC weight concentration is of 2.0 wt %. Compared with PNIPAM, perhaps because the fiber and stimulus responsive high-molecular interaction is small, the mechanical properties improve the effect is embodiment 1 is small. The resulting stimulus responsive material in the 25 has fluidity [...] , storage elastic modulus of 57 Pa. If heating, in about 60 the solid is formed under [...] gelationus, 30-60 the maximum [...] the storage elastic modulus of the 60 for [...] 2920 Pa. Should be note, 30-45 the maximum [...] the storage elastic modulus of the 45 for [...] 157 Pa. Furthermore, attached to the heated to the 70 the standard agar culture medium [...] , and observe the shape change, the result does not display mobility to be transformed into a solid gel. The results recorded in table 1.

Should be note, the SP value of MC (-CH-CH (OCH₃)-CH (OH)-CH (O-)-CH (CH₂ OH)-O-) unit calculates the 31.4, SP value differences to 6.8.

Embodiment 3

The polylactic acid (PLA) (70 wt %)PET and copolymerization (glycol with a dicarboxylic acid (terephthalic acid 61.25mol %, isophthalic acid 26.25mol %, 5-sulfoisophthalic acid sodium (SSIA) 12.5mol %)random copolymer) (30 wt %)melt, the use of sea-island distribution type spray nozzle after spinning, stretch to 4.4 times, get 68dtex -15 the fibrous island composite fiber.

The resulting island composite fiber length measurer grips ties , with the guillotine type cutting machine cut into the fiber length is 1.0 mm, with the 70 water [...] 5 minutes heat treatment, to dissolve and remove the sea component. Then wash, PLA fiber obtained. The cross section of the observation of the fiber, the fiber diameter of the average result number 570 nm.

The resulting fiber and water in the beater to the beating in Niagara, PFI mill and further the beating, in the recycled fiber, fiber concentration obtained 8.4 wt % fiber and water mixture. And then, join the mixture 23.8g and a nonionic surfactant (polyoxyethylene styrene ether) and water, into the high-speed mixer, to 13900rpm for 30 minutes, the fiber dispersion.

In the thus-obtained in fiber dispersion, by adding reference known method (Macromol.   Res.,   10,   6 (2002)) the stimulus responsive polymer (PLA-PEG-PLA) triblock copolymer (Mn   4420, PLA/PEG (w/w) = 66/34), the stimulus responsive material. At this moment, the quantity of the fiber average single fiber diameter is 570 nm, L/D to 1754, the weight concentration is 0.9 wt %, stimulus responsive high molecular weight concentration is 15 wt %, stimulus responsive polymer/fiber ratio is 17, surface active agent concentration is 0.9 wt %.

The resulting stimulus responsive material in the 25 has fluidity [...] , storage elastic modulus is 80 Pa. Furthermore, if, the heating into a solid gel. 30-60 the under [...] the maximum storage elastic modulus at about 33 the lower display [...] to 380 Pa. The results recorded in table 1.

Should be note, the SP value of the PLA (-CH (CH₃)-CO-O-) unit calculates the 22.8, stimulus responsive polymer of the SP value (-CH (CH₃)-CO-O-) unit (22.8 SP value) and (-(CH₂)₂-O-) unit (19.2 SP value) is 66/34 to calculate the rate of 21.6, SP the value 1.2. On the other hand, stimulus responsive polymer and the fiber have a common basic chemical structure, as a major chemical structure through (-CH (CH₃)-CO-O-) unit to carry out the calculation, the SP value is 22.8, SP to the value 0.

Embodiment 4

The PLA fiber concentration to be 0.6 wt %, in addition to the embodiment 3 of the same. At this moment, the number of composite material the average single fiber diameter is 570 nm, L/D to 1754, the weight concentration is 0.6 wt %, stimulus responsive high molecular weight concentration is 15 wt %, stimulus responsive polymer/fiber ratio of 25, the surfactant concentration is 0.9 wt %.

The resulting stimulus responsive material in the 25 has fluidity [...] , storage elastic modulus is 17 Pa. Furthermore, the 30-45 under [...] the maximum storage elastic modulus at about 35 the lower display [...] to 135 Pa.

The concentration of PLA fibers with 0.9 wt % compared with, perhaps because the fiber concentration becomes small, so the stimulus responsive polymer reinforcing effect is not full, the embodiment of the storage elastic modulus is 3 small.

Embodiment 5

With the embodiment of the 3 same PLA (70 wt %)and copolymerized PET (30 wt %)melt. Furthermore, using the island distribution nozzle is spinning, stretch to 4.4 times, get 45dtex -10 filamentary island composite fiber.

The resulting island composite fiber length measurer grips ties , with the guillotine type cutting machine cut into the fiber length is 1.5 mm, with the 70 water [...] 5 minutes heat treatment, to dissolve and remove the sea component. Then wash, to obtain polylactic acid fiber. The cross section of the observation of the fiber, the fiber diameter is the average number of 810 nm.

The resulting fiber and water in the beater to the beating in Niagara, PFI mill and further the beating, in the recycled fiber, fibrous and water mixture. And then, join the mixture and a nonionic surfactant (polyoxyethylene styrene ether, a number average molecular weight of 1 million) and water, into the high-speed mixer, to 13900rpm for 30 minutes, the fiber dispersion.

In the thus-obtained in fiber dispersion, accession to embodiment 3 of the used in the stimulus responsive polymer (PLA-PEG-PLA) triblock copolymer, the stimulus responsive material. At this moment, the number of composite material the average single fiber diameter is 810 nm, L/D to 1852, the weight concentration is 0.9 wt %, stimulus responsive high molecular weight concentration is 15 wt %, stimulus responsive polymer/fiber ratio is 17, surface active agent concentration is 0.9 wt %.

The resulting stimulus responsive material in the 25 has fluidity [...] , storage elastic modulus is 32 Pa. Furthermore, the 30-60 under [...] the maximum storage elastic modulus at about 35 the lower display [...] to 124 Pa.

Fiber concentration and the embodiment 3 is the same, but is perhaps because the average number of large diameter fibers, dispersibility is low, therefore the largest embodiment of the storage elastic modulus is 3 small.

Embodiment 6

As a stimulus responsive polymer poly (N-isopropyl acrylamide) ; (PNIPAM) ([...] (strain) systems, Mn2 million -2.5 million) to the amount of the change, in addition, with the embodiment 3 of the same. At this moment, the number of composite material the average single fiber diameter is 570 nm, L/D to 1750, the weight concentration is 0.9 wt %, stimulus responsive high molecular weight concentration is 10 wt %, stimulus responsive polymer/fiber ratio is 11, the surfactant concentration is 0.9 wt %.

The resulting stimulus responsive material in the 25 has fluidity [...] , storage modulus of elasticity of 70 Pa. Furthermore, if, the heating into a solid gel. 30-60 the maximum [...] the storage elastic modulus of about 45 the for [...] 88 Pa, after gelation, the storage elastic modulus of the largest, when alone PNIPAM compared with the display for higher value, but higher than that of embodiment 3 is small.

Should be note, the SP value of the PLA (-CH (CH₃)-CO-O-) unit calculates the 22.8, PNIPAM of the SP value (-CH₂-CH-CONH-CH (CH₃)₂-) unit calculates the 24.6, SP value is 1.8.

Comparative example 1

In addition to not add fiber and other than a nonionic surfactant, with the embodiment 1 to the same as. PNIPAM is added into the water, to obtain high-molecular material. At this time the weight of the PNIPAM a concentration of 10 wt %. The resulting high molecular material in the 25 has fluidity [...] , at about, the heating if the 35 [...] form a solid gel. However, storage elastic modulus is small.

Comparative example 2

In addition to not add fiber and other than a nonionic surfactant, with the embodiment 3 of the same. Adding the embodiment 3 of the used in the triblock copolymer (PLA-PEG-PLA), to obtain high-molecular material. At this moment, stimulus responsive high molecular weight concentration is 15 wt %. The resulting high molecular material in the 25 has fluidity [...] , if, the heating form a solid gel. But 30-60 the under [...] the maximum storage elastic modulus at about 34 the for [...] 47 Pa, is relatively small.

Comparative example 3

In addition to not add fiber and other than a nonionic surfactant, and embodiment 7 to the same as. MC is added into the water, to obtain high-molecular material. At this moment of the weight concentration of the MC 2.0 wt %. The resulting high molecular material in the 25 has fluidity [...] , at about, the heating if the 60 [...] form a solid gel, but the maximum storage elastic modulus is small.

Comparative example 4

In addition to the outside without adding PNIPAM, with the embodiment 1 to the same as. At this time the weight of the fiber concentration is 1.0 wt %. The resulting fiber dispersion material does not display temperature responsive, mechanical characteristics is very low.

Comparative example 5

As fiber, is changed into the 22dtex -20 single strand (monofilament titer 1.1dtex, the diameter of the the 11.1  m) of N6 fiber cut to 1.00 mm are, in addition, with the embodiment 1 to the same as. Stimulus responsive material at this moment the weight concentration is 1.0 wt %, weight of surface active agent concentration is 1.0 wt %, PNIPAM the weight concentration of the 10 wt %. Can know the resulting stimulus responsive material in the 25 has fluidity [...] , if heating is carried out at about 35 the display forming a slightly [...] gelationus fluidity, but the greatest PNIPAM storage elastic modulus than the case of separate small, could not be confirmed to the fiber reinforcing effect brought about by.

Comparative example 6

In addition to the fiber is set to 10 wt % other than, and comparative example 4 the same processing. Stimulus responsive material at this moment the weight concentration is 10 wt %, weight of surface active agent concentration is 1.0 wt %, PNIPAM the weight concentration of the 10 wt %. The fiber is not dispersed and separate, almost non-display temperature responsive. Furthermore, also it is unable to determine the storage elastic modulus.

Comparative example 7

PLA fiber replaced, adding silicon dioxide particles (diameter of about 100 nm) (" SNOWTEX   MP1040 the [...] Nissan chemical (strain) systems) 1.0 wt %, in addition, with the embodiment 3 of the same. The results of storage elastic modulus of the largest known a stimulus responsive polymer separate Case reduced.

<test example 2>

Using embodiment 3, 5, comparative example 2 obtained in the anti-adhesion effect of the material evaluated. Results shown in table 2. The embodiment of the invention of the stimulus responsive material of the anti-adhesion effect excellent, but comprises a stimulus responsive polymer gel material in separate cases, not be able to achieve its effect.

[Table 1]

[Table 2]

Industrial practicability

The invention can be used as the application which combines the convenience and mechanical properties of the stimulus responsive material and using the medical material.