JP4549410B2 - Polymer gel composite and method for producing the same - Google Patents

Description

  The present invention relates to a polymer gel composite and a method for producing the same.

  The polymer gel has a three-dimensional network structure in which polymers are cross-linked, and is a substance containing a large amount of liquid inside. As a result, the polymer gel in an intermediate state between solid and liquid has non-fluid but elastic properties similar to rubber, and also has excellent properties not found in solid materials including permeability and flexibility. Have. Further, the toxicity to the living body is low, that is, the biocompatibility is good. Therefore, polymer gels are widely used from industrial to medical fields such as adhesive sheets, water-absorbing materials, or contact lenses.

  Further, the polymer gel has a very small friction coefficient on the surface as compared with other solid materials. Therefore, application of polymer gel to bearings and artificial joints that require low friction is expected. Among these, polymer gels are useful for biomaterials that require biocompatibility such as artificial joints. As described above, recently, various polymer gels are used as polymer gel composites by bonding polymer gels to various polymer base materials such as engineering plastic (engineering plastic) members constituting bearings and cartilage in artificial joints instead of simple substances. Consideration is being made. In the following description, the polymer substrate is simply referred to as a substrate.

  In the polymer gel composite, the degree of adhesive strength between the polymer gel and the substrate is important. For example, since a high load is always applied to a sliding portion of a bearing or an artificial joint, it is necessary to maintain an adhesive strength that can withstand the load. However, a polymer gel having characteristics such as elasticity and deformability is not only unstable in shape but also in a very wet state, so that it is difficult to adhere to a substrate with a general-purpose adhesive.

  Some general purpose adhesives may be used to adhere gels, such as special purpose adhesives for attaching tissue in surgery. However, the polymer gel easily absorbs the adhesive due to its molecular structure. For this reason, the adhesive that has penetrated into the interior of the polymer gel is solidified to change the composition of the polymer gel, resulting in a problem that properties and appearance are significantly impaired. Therefore, it is preferable to produce the polymer gel composite without using an adhesive.

Thus, a method for bonding a substrate and a polymer gel without using an adhesive is desired. For example, after applying a composition containing a hydrogel-forming polymer and a photopolymerization initiator to the surface of the substrate, a polymer gel is formed on the surface of the substrate by irradiating electromagnetic radiation from ultraviolet to visible light. A method has been proposed (see, for example, Patent Document 1).
JP-T-2006-504451

  However, the means described in Patent Document 1 is a method of immobilizing the hydrogel disposed on the surface of the base material, but cannot sufficiently increase the adhesive strength between the base material and the hydrogel. In other words, Patent Document 1 discloses a method suitable for surface modification of a base material in which adhesive strength is not a problem, such as biocompatibility and wettability of a base material such as a catheter or a stent. However, on the other hand, since a high load is continuously applied like a sliding part, it is difficult to apply as an adhesion technique for a polymer gel composite that requires high adhesive strength.

  Accordingly, an object of the present invention is to provide a method for producing a polymer gel composite by adhering a ready-made substrate and a polymer gel without using an adhesive. By using this method, a polymer gel composite in which the base material and the polymer gel are firmly bonded can be provided.

  As a result of intensive studies, the present inventors have arranged a cross-linked polymer impregnated with a monomer on the surface of the base material on which a polymerization initiator is arranged; by polymerizing the monomer impregnated with the cross-linked polymer, The present invention was completed by finding that a “polymer gel composite” in which the polymer gel was bonded to the polymer gel was obtained.

The first of the present invention relates to the polymer gel composite shown below.
[1] A polymer gel composite comprising a polymer substrate and a polymer gel having an IPN structure adhered to the polymer substrate, the polymer substrate and the polymer being measured by the following method A polymer gel composite having an adhesive strength A with a gel of 0.5 N / cm to 50 N / cm.
[Measurement method of adhesive strength A]
Peeling off an end portion of an adhesive portion between the polymer gel contained in the polymer gel composite in an atmospheric environment and the polymer substrate;
Inserting a stripping member with a sharp tip (10 °) into the gap between the polymer gel at the peeled end and the polymer substrate;
By pressing the stripping member against the site where the polymer gel and the polymer base material have been peeled off, all of the polymer gel is stripped from the polymer base material. Measuring the pressing force until all of the molecular gel is removed from the polymer substrate;
The result of calculation using the following formula (1) from the average value M (N) of the maximum value and the minimum value of the measured pressing force is defined as adhesive strength A.
Adhesive strength A (N / cm) = M × tan 10 ° / L (1)
However, M is an average pressing force value (N), and L is a width (cm) of the peeled adhesive portion.
[2] A polymer gel composite comprising a polymer substrate and a polymer gel having an IPN structure adhered to the polymer substrate, the polymer substrate and the polymer being measured by the following method A polymer gel composite having an adhesive strength B with a gel of 0.1 N / cm to 25 N / cm.
[Measurement method of adhesive strength B]
The polymer gel contained in the polymer gel composite is hydrated to achieve equilibrium swelling;
Peeling off the end of the bonded portion between the equilibrium swollen polymer gel and the polymer substrate;
Inserting a stripping member with a sharp tip (10 °) into the gap between the polymer gel at the peeled end and the polymer substrate;
By pressing the stripping member against the site where the equilibrium swollen polymer gel and the polymer substrate are peeled off, the polymer gel is completely peeled off from the polymer substrate, and the pressing of the stripping member is started. To measure the pressing force until all of the polymer gel is peeled off from the polymer substrate;
The result of calculation using the following equation (2) from the average value M (N) of the maximum value and the minimum value of the measured pressing force is defined as adhesive strength B.
Adhesive strength B (N / cm) = M × tan 10 ° / L (2)
However, M is an average pressing force value (N), and L is a width (cm) of the peeled adhesive portion.
[3] The polymer gel composite according to [1] or [2], wherein a water-insoluble polymer exists between the polymer substrate and the polymer gel.
[4] The polymer gel composite according to any one of [1] to [3], wherein the water content of the polymer gel is 10% by weight to 99% by weight.
[5] The polymer gel composite according to any one of [1] to [4], wherein the polymer gel contains water.
[6] The polymer gel composite according to any one of [1] to [4], wherein the polymer gel includes a non-volatile liquid such as glycerin.
[7] Any one of [1] to [6], wherein the polymer gel has an IPN structure including a polymer having a crosslinked structure and a polymer having a crosslinked structure or a non-crosslinked structure independent of the polymer. The polymer gel composite according to 1.

The second of the present invention relates to a method for producing a polymer gel composite shown below.
[8] A method for producing a polymer gel composite comprising a polymer substrate and a polymer gel having an IPN structure adhered to the polymer substrate,
Preparing a first molded article comprising a crosslinked polymer impregnated with a monomer, a polymerization initiator and a liquid, and optionally a crosslinking agent; at least a part of the surface is covered with a film containing a photopolymerization initiator Preparing a second molded product; and irradiating the first molded product overlaid on the film containing the photopolymerization initiator with light having a wavelength necessary for polymerization. A method for producing a composite.
[9] The method for producing a polymer gel composite according to [8], wherein the monomer is a non-electrolyte.

  According to the present invention, a polymer substrate and a polymer gel can be bonded without using an adhesive. According to the present invention, a polymer gel composite exhibiting high adhesive strength can also be obtained. The polymer gel composite obtained by the present invention has low friction derived from the polymer gel and can also have high adhesive strength. Therefore, it is also useful as a sliding member for artificial joints and bearings that are subjected to high loads.

  FIG. 1 is a schematic view of an example of a polymer gel composite according to the present invention. The composite 10 is composed of a base material 11 and a polymer gel 12. In the following description, the polymer gel composite of the present invention is also simply referred to as “composite”.

  The base material 11 is a molded polymer member, and also acts as a support for fixing the polymer gel 12. The polymer that is the material of the substrate 11 is not particularly limited, and may be appropriately selected according to the use of the composite 10. Examples of such polymers include general purpose plastics such as low density polyethylene (LDPE), high density polyethylene (HDPE), polystyrene (PS), polypropylene (PP). In addition, when the composite 10 is used for a medical part such as an artificial joint, the base 11 is preferably made of ultrahigh molecular weight polyethylene or the like; when the composite 10 is used for an industrial article, the base 11 is used. It is preferable to use engineering plastics or super engineering plastics.

  Engineering plastic is usually a resin having a heat resistance temperature of 100 ° C. or higher and a certain mechanical strength; super engineering plastic means a resin having a heat resistance temperature of 150 ° C. or higher among engineering plastics. Examples of engineering plastics suitable for the present invention include polyacetal (POM), polyamide (PA), polycarbonate (PC), modified polyphenylene ether (m-PPE), polybutylene terephthalate (PBT), GF reinforced polyethylene terephthalate (GF-PET). ), Ultra high molecular weight polyethylene (UHPE).

  Examples of super engineering plastics include polyarylate (PAR), polysulfone (PSF), polyethersulfone (PES), polyphenylene sulfide (PPS), polyetheretherketone (PEEK), polyimide (PI), polyetherimide ( PEI), fluororesin, and liquid crystal polymer (LCP).

  The polymer gel 12 has an IPN structure. The IPN structure refers to a structure in which two or more kinds of polymers are intermingled with each other without forming a chemical bond with each other. The polymer gel 12 can have an IPN structure in which polymers having a crosslinked structure (crosslinked polymers) are combined; or an IPN structure in which a crosslinked polymer and a polymer having a non-crosslinked structure (noncrosslinked polymer) are combined. Since the polymer gel 12 having an IPN structure is in a state in which another polymer is entangled with a network-like cross-linked polymer, the polymer gel 12 can exhibit high strength while maintaining characteristics as a polymer gel such as high deformability. Among them, the polymer gel 12 having an IPN structure in which a flexible, chain-like non-crosslinked polymer is entangled with a rigid network-like crosslinked polymer can have very high strength. This is useful when applied to a sliding part where a high load is applied.

The thickness t1 of the polymer gel 12 is preferably 1 × 10 ⁻³ mm or more. If the thickness is less than 1 × 10 ⁻³ mm, it may be difficult to maintain the characteristics of the polymer gel 12 over a long period of time from the viewpoint of wear resistance. The upper limit of the thickness t1 is not particularly limited, and may be set as appropriate according to the use of the composite.

The polymer gel 12 contains a liquid (solvent). The liquid of the polymer gel 12 is not particularly limited, and may be appropriately selected according to the use of the composite. When the composite is applied to a biomaterial, a liquid having high biocompatibility, for example, water (particularly pure water or physiological saline) may be selected.
The liquid of the polymer gel 12 may be a non-volatile liquid such as glycerin. If a non-volatile liquid is selected, the wet state inside the polymer gel can be maintained for a long period of time, making it difficult to dry. Therefore, in the case of a composite for industrial use that can be used in a dry environment with low humidity, it is preferable to use these high-boiling liquids as polymer gel liquids. Since glycerin is unsuitable for biomaterials that require biocompatibility, it is preferable to refrain from use when biocompatibility is required.
The polymer gel 12 containing the non-volatile liquid is obtained by immersing the composite 10 having the polymer gel 12 containing water in a non-volatile liquid stock solution or an aqueous solution, and rinsing the water of the polymer gel 12 with a non-volatile liquid (glycerin). Can be obtained by partial or total substitution.

  Moreover, the ratio of the liquid contained in the polymer gel 12 is not particularly limited, but for example, the water content (the ratio of water contained in the polymer gel) is preferably 10% by weight or more and 99% by weight or less. Furthermore, the water content of the polymer gel 12 is preferably 50% by weight or more, and may be even higher. The polymer gel 12 having a water content of 50% by weight or more maintains a very high wet state. The polymer gel 12 that has been swelled in equilibrium with water preferably has a degree of swelling of 2 or more and a water content of 50% by weight or more.

  The moisture content of the polymer gel 12 is shown on a dry basis (dry basis moisture content). The moisture content shown on a dry basis means the ratio (% by weight) of the weight of water contained in the polymer gel 12 with respect to the weight of the polymer gel 12 in a water-containing state. The moisture content is measured, for example, by taking a part of the polymer gel 12 as a sample; weighing this sample (W1 weight); drying the sample with a heat drying apparatus such as an oven; weighing the sample after drying (W2). Weight). The drying time and temperature are not particularly limited. The moisture content based on the dry weight of the polymer gel is calculated from the formula {(W2-W1) / W1} × 100.

  On the other hand, the swelling degree of the polymer gel is such that the weight of the dry polymer gel 12 containing no liquid is x1, and the weight of the polymer gel 12 containing a liquid (for example, water) is x2. Calculated as “x2 / x1”.

The crosslinked polymer which is one component constituting the IPN structure of the polymer gel can be preferably produced by radical copolymerization of two or more types of monomers having different reactivities. Moreover, it is preferable that the equilibrium swelling degree of the crosslinked polymer by a good solvent is 5-1000, and the weight content rate of a good solvent is 50-99.9 weight%.
The equilibrium swelling degree and rigidity of the crosslinked polymer can be controlled by adjusting the degree of crosslinking. What is necessary is just to adjust a crosslinking degree with the quantity of a crosslinking agent. For example, in the case of using a crosslinked polymer obtained by irradiating light to a monomer composition containing a photopolymerization initiator, the degree of crosslinking is controlled by appropriately adjusting the concentration of the crosslinking agent contained in the monomer composition. be able to.

  The non-crosslinked polymer means a polymer obtained by using a monomer or polymer that does not use a crosslinking agent and does not have self-crosslinking property. The degree of crosslinking of the crosslinked polymer and the non-crosslinked polymer is calculated from the amount of the crosslinking agent added when the monomer is polymerized.

  The substrate 11 may have a polymerization layer 14 on the surface to be bonded to the polymer gel 12. The polymerization layer 14 is a surface layer of the base material 11 and is a layer that is invaded by a part of the polymer constituting the polymer gel 12. The base material 11 and the polymer gel 12 are bonded to each other with the polymer layer 14 as a bridge. Therefore, the superposition | polymerization layer 14 can also mutually adhere firmly. The shear bond strength between the base material 11 and the polymer gel 12 of the composite 10 can be adjusted within the range of 0.1 N / cm or more and 50 N / cm or less, and can also be made high adhesive strength. The shear bond strength can be measured according to JIS-K-6850 (1999). In FIG. 1, the boundary line between the polymer layer 14 and the base material 11 and the polymer gel 12 is shown. As described above, the polymer layer 14 enters the base material 11 and the polymer gel 12. In reality, it may be difficult to confirm a clear boundary line.

  Whether or not the polymer constituting the polymer gel 12 has invaded the polymer layer 14 is determined by removing the polymer gel 12 from the composite 10 and exposing the adhesive interface between the base material 11 and the polymer gel 12. And the exposed interface can be confirmed by IR measurement.

  In the composite of the present invention, the polymer gel only needs to be adhered to the surface of the polymer substrate, and the polymer gel may be adhered to both surfaces of the polymer substrate; Two or more polymer substrates and two or more polymer gels may be laminated alternately; other structures may be adhered to each other via a molecular gel.

  Further, a water-insoluble polymer may be present near the interface where the substrate 11 and the polymer gel 12 are bonded. The water-insoluble polymer is a polymer used for disposing a polymerization initiator on the surface of the substrate 11 before adhesion in the production process (described later) of the composite of the present invention. Examples of water insoluble polymers include polyvinyl acetate.

  The adhesive strength between the polymer gel 12 of the composite 10 and the substrate 11 can be adjusted as appropriate. For example, as will be described later, the adhesive strength can be adjusted by adjusting the amount of the polymerization initiator disposed on the substrate 11. For example, two types of adhesive strength (adhesive strength A and adhesive strength B) measured by the following procedure can be adjusted to arbitrary strengths. The adhesive strength A indicates the adhesive strength of the composite of the present invention under a normal environment. For example, the adhesive strength A may be an adhesive strength immediately after production of the composite or an adhesive strength of a composite (which may be in a substantially dry state) left for a long time in an air atmosphere. The adhesive strength B indicates the adhesive strength when the polymer gel of the composite of the present invention is hydrated and in equilibrium swelling. The adhesive strength B includes, for example, the adhesive strength of a composite used in an aqueous environment, that is, the adhesive strength of a composite used as a member of an artificial joint in vivo.

  The adhesive strength A can be at least 0.1 to 10 N / cm, can be 0.1 to 25 N / cm, and can also be 0.1 to 50 N / cm. On the other hand, the adhesive strength B can be at least 0.1 N / cm to 5 N / cm, can also be 0.1 N / cm to 15 N / cm or less, and further can be 0.1 N / cm to 25 N / cm or less. It is also possible.

  In order to increase the adhesive strength A and the adhesive strength B, as will be described later, the amount and concentration of the photopolymerization initiator disposed on the surface of the polymer substrate are increased. Other: Increase the monomer concentration of the cross-linked polymer that is the first molded product (for example, the concentration of the monomer contained in the polymerization solution) and the cross-linking density (If excessively increased, the adhesive strength may decrease on the contrary) Changing the type of monomer impregnated in the first molded product, or increasing the concentration of the monomer or the crosslinking agent (if excessively increased, the adhesive strength may decrease); Improvement of the level of removal of dissolved oxygen (for example, after making the inside of the vacuum chamber a high vacuum, replace with an inert gas to remove oxygen from the polymerization system); polymer gel and polymer group in the bonding process To increase the adhesion between, it may be employed means such as.

The procedure for measuring the adhesive strength A is as follows: the polymer gel contained in the polymer gel composite in the atmospheric environment is peeled off the end of the bonded portion with the polymer substrate; the polymer gel at the peeled end; Then, a stripping member having a sharp tip (set to 10 °) is inserted into the gap with the polymer substrate; and the stripping member is pressed against the site where the polymer gel and the polymer substrate are stripped. To measure all the polymer gel from the polymer substrate, and measure the pressing force from the start of pressing the stripping member until all of the polymer gel is separated from the polymer substrate; The average value M (N) of the maximum value and the minimum value of the pressed force is substituted into the following formula (1) to determine the adhesive strength A. In the formula (1), the width of the adhesive part peeled off by the peeling member (the length of the adhesive part in contact with the tip of the peeling member) is defined as L (cm).

Adhesive strength A (N / cm) = M × tan 10 ° / L (1)

The procedure for measuring the adhesive strength B is as follows: the polymer gel of the polymer gel composite is hydrated to achieve equilibrium swelling; the end of the adhesion portion between the equilibrium swollen polymer gel and the polymer substrate is peeled off; A stripping member having a sharp tip (set to 10 °) is inserted into the gap between the polymer gel at the peeled end and the polymer base material; the stripping member is subjected to the equilibrium swelling By pressing against the site where the molecular gel and the polymer substrate are peeled off, all of the polymer gel is peeled from the polymer substrate, and from the start of pressing of the stripping member, all of the polymer gel is The pressing force until peeling from the material is measured; the average value M of the measured maximum and minimum values of the pressing force is substituted into the following formula (2) to determine the adhesive strength B. In the formula (2), the width of the adhesive part peeled off by the peeling member (the length of the adhesive part in contact with the tip of the peeling member) is defined as L (cm).

Adhesive strength B (N / cm) = M × tan 10 ° / L (2)

  Below, the measuring method of adhesive strength A and adhesive strength B is demonstrated more concretely.

[Measurement of adhesive strength A and adhesive strength B]
The measurement of the adhesive strength A and the adhesive strength B is performed using the apparatus shown in FIG. The measuring device 20 is a load cell 22 fixed to a movable table 21 that can be freely moved up and down; a sample for measuring adhesive strength, and a T on which a composite 23 composed of a polymer gel and a polymer substrate is fixed. A jig 24; a scraper 26 for stripping a polymer gel from a polymer substrate; and a fixing base 28 to which the scraper 26 is fixed.

  The complex 23 as a measurement sample is obtained by a complex production method described later. When measuring the adhesive strength A, a composite immediately after production may be used as a sample, or a composite in a normal atmospheric environment may be used as a measurement sample. Moreover, when measuring the adhesive strength B, the composite 23 may be immersed in water before the measurement, and the polymer gel may be hydrated until equilibrium swelling is obtained as a measurement sample. The time for immersing the polymer gel in water is not particularly limited, and is appropriately determined according to the volume of the polymer gel. In order to sufficiently hydrate the polymer gel to achieve equilibrium swelling, depending on the thickness of the gel and the properties of the polymer constituting the gel, for example, if the main component is a strong electrolyte and the thickness is about 2 mm The composite 23 may be immersed in water for about 1 day.

  Further, before measuring the adhesive strength, the end portion of the adhesive surface between the polymer gel (equilibrium swollen in the case of the adhesive strength B) and the polymer substrate is peeled off. The tip of the scraper 26 is pressed against the gap between the polymer gel and the polymer substrate at the peeled end. What is necessary is just to perform suitably using a cutter etc. in order to peel a polymer gel from a polymer base material. It is only necessary to form a gap that can press the peeling member (for example, the scraper 26) by peeling off the end of the bonding surface.

  When measuring the adhesive strength of the composite body 23, first, the composite body 23 is attached to a predetermined position of the T-shaped jig 24. It is preferable to adjust and attach so that the width direction of the composite 23 and the width direction of the scraper 26 are substantially parallel. Subsequently, as shown in FIG. 2B, the tip of the scraper 26 is pressed against the gap between the peeled polymer gel and the polymer substrate. At this time, it is not necessary to strongly press the tip of the scraper 26 against the peeled portion, and the tip may be lightly touched.

  Next, the moving base 21 is gradually lowered (in the direction of the arrow), and the polymer gel is peeled off from the polymer base material by the scraper 26. The moving table 21 is lowered until all of the polymer gel is peeled off from the polymer substrate. The pressing force is measured after the moving table 21 starts to descend (starts pressing) until all of the polymer gel is peeled off from the polymer substrate. The average value of the maximum value m1 and the minimum value m2 of the measured pressing force is defined as the adhesive strength. Further, when the above pressing force becomes free, it means that all of the polymer gel is peeled off from the polymer substrate.

  When the adhesive strength is measured, the adhesive interface between the polymer substrate and the polymer gel is not stable until a certain time has elapsed from the start of pressing, and the measured pressing force may be blurred. Therefore, it is preferable that the maximum value m1 and the minimum value m2 of the pressing force for obtaining the adhesive strength are obtained from the pressing force measured in a stable state with no pressing force fluctuation after a certain time has elapsed from the start of pressing.

  As shown in FIG. 3, the scraper 26 used for measuring the adhesive strength is a peeling member made of metal or plastic. The angle θ of the tip of the scraper 26 is an acute angle, which facilitates peeling of the polymer gel from the polymer substrate. The tip angle θ is not particularly limited as long as it is smaller than a right angle, but is usually 10 °.

  The width L1 of the scraper 26 is preferably substantially the same as or larger than the width of the polymer gel that constitutes the composite to be the measurement sample. Thereby, since the whole width | variety area of a polymer gel can be peeled uniformly from a polymer base material, the variation in the measured pressing force can be suppressed. The thickness t3 of the scraper 26 and the thickness t2 of the blade at the tip thereof are not particularly limited, and may be set as appropriate according to the thickness of the polymer gel used.

  Although the composite_body | complex of this invention can be manufactured by arbitrary methods, as long as the effect of this invention is not impaired, it is manufactured by the method shown below, for example.

  The method for producing a composite according to the present invention is a method for producing a polymer gel composite in which a polymer gel having an IPN structure is bonded to a polymer substrate, wherein (1) a monomer, a polymerization initiator and a liquid, A step of preparing a first molded article containing a crosslinked polymer impregnated with a crosslinking agent if necessary; (2) a second molded article in which at least a part of the surface is covered with a film containing a photopolymerization initiator; And (3) irradiating light onto the first molded product overlaid on the surface of the film.

  In the step (1), a first molded product containing a crosslinked polymer impregnated with a monomer, a polymerization initiator and a liquid, and, if necessary, a crosslinking agent is prepared. When the first molded product is stacked on the base material that has been subjected to the predetermined treatment; and when the first molded product stacked on the base material is irradiated with light, the polymer that is a polymer of the monomer is converted into a crosslinked polymer. The polymer gel is entangled and has an IPN structure. The first molded product may be a crosslinked polymer impregnated with a monomer, a polymerization initiator and a liquid, and if necessary, a crosslinking agent, or the monomer, the polymerization initiator and a liquid, and optionally crosslinked. It may be a crosslinked polymer having an IPN structure impregnated with an agent. The crosslinked polymer having an IPN structure means a polymer in which another polymer is entangled with the crosslinked polymer.

  Examples of the crosslinked polymer contained in the first molded product include 2-acrylamido-2-methylpropanesulfonic acid (AMPS), acrylamide (AAm), acrylic acid (AA), methacrylic acid, N-isopropylacrylamide, and vinylpyridine. , Hydroxyethyl acrylate, vinyl acetate, dimethylsiloxane, styrene (St), methyl methacrylate (MMA), trifluoroethyl acrylate (TFE), styrene sulfonic acid (SS), dimethylacrylamide (DMAAm), hydroxyethyl methacrylate (HEMA), etc. And a crosslinked polymer obtained by post-crosslinking a polymer such as polyvinyl alcohol.

  Further, the crosslinked polymer contained in the first molded product may be a polysaccharide such as gellan, hyaluronic acid, carrageenan, chitin or alginic acid, or a protein such as gelatin or collagen. If these are used, the biocompatibility of the obtained composite can be improved.

  The crosslinked polymer can be preferably produced by radical copolymerization of two or more monomers having different reactivities. The crosslinked polymer preferably has an equilibrium swelling degree of 5 to 1000 with a good solvent and a weight content of the good solvent of 50 to 99.9% by weight.

The cross-linking mode of the cross-linked polymer is not necessarily a chemical cross-linking by a covalent bond. For example, physical cross-linking by hydrogen bond or ionic bond may be used. When preparing a first molded article containing a polymer capable of crosslinking by hydrogen bonding (for example, polyvinyl alcohol (PVA)) as a crosslinked polymer, a solvent (not limited to water) necessary to form a crosslinking with the polymer. And a polymer contained in the solution may be cross-linked by a freeze-thaw method or the like.
On the other hand, when preparing a first molded product containing a polysaccharide or protein (for example, agar or gelatin) capable of crosslinking by hydrogen bonding as a crosslinked polymer, a solvent necessary for forming a crosslink with the polysaccharide or protein. Is prepared, and this solution is cooled to crosslink the polysaccharide or protein contained in the solution.

  As described above, the crosslinked polymer contained in the first molded product may have an IPN structure by being intertwined with another polymer. Examples of other polymers include non-electrolyte non-crosslinked polymers. Examples of monomers that form this non-crosslinked polymer include fluorine-containing monomers, specifically 2,2,2-trifluoroethyl methyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 3- (Perfluorobutyl) -2-hydroxypropyl methacrylate, 1H, 1H, 9H-hexadecafluorononimethacrylate, 2,2,2-trifluoroethyl acrylate, 2,3,4,5,6-pentafluorostyrene and fluoride Contains vinylidene.

  Examples of monomers impregnated in the first molded product include 2-acrylamido-2-methylpropanesulfonic acid (AMPS), acrylamide (AAm), acrylic acid (AA), methacrylic acid, N-isopropylacrylamide, and vinylpyridine. , Hydroxyethyl acrylate, vinyl acetate, dimethylsiloxane, styrene (St), methyl methacrylate (MMA), trifluoroethyl acrylate (TFE), styrene sulfonic acid (SS) and dimethylacrylamide.

  In addition, the monomer solution may contain a crosslinking agent or a photopolymerization initiator depending on the application. However, in order to obtain low friction of the polymer gel of the composite to be produced, it is better not to use a crosslinking agent or to lower the concentration of the crosslinking agent. This is because a low friction property can be obtained when the polymer gel has an IPN structure composed of a crosslinked polymer and a non-crosslinked polymer. A photoinitiator and a crosslinking agent are not specifically limited, A well-known thing is used. The crosslinking agent only needs to be able to crosslink the monomer contained in the first molded product, and examples thereof include N, N′-methylenebisacrylamide (MBAA) and ethylene glycol dimethacrylate. On the other hand, the photopolymerization initiator contained in the monomer solution may be the same agent as the photopolymerization initiator (described later) disposed on the substrate in the step (2), or other initiator (benzoin methyl). Ether and 2-oxoglutaric acid: 2-OGA).

  The method for impregnating the crosslinked polymer with the monomer is not particularly limited. For example, the monomer-impregnated object such as the crosslinked polymer may be immersed in a solution containing the monomer for a certain period of time. The time for immersing the monomer-impregnated object in the monomer solution may be appropriately determined according to the volume of the monomer-impregnated object.

  The liquid contained in the first molded product is not particularly limited and may be appropriately selected depending on the application, but examples include water.

  In the step (3) described later, a monomer contained in the first molded product is polymerized to form a polymer gel. In order to increase the strength of the polymer gel, the monomer contained in the first molded product is a non-electrolytic monomer, or the polymer polymerized in the step (3) is a non-crosslinked polymer (that is, the first It is preferable that no cross-linking agent is added to the molded product 1.

  In the step (2), a second molded product is prepared in which the surface to which the polymer gel is adhered is covered with a film containing a photopolymerization initiator. The second molded product is a polymer substrate for bonding with the polymer gel. The film is a resin film in a dry state containing a photopolymerization initiator. In the following description, the adherend surface of the substrate for adhering the polymer gel is also simply referred to as “adherence surface”.

  Examples of methods for forming a film containing a photopolymerization initiator on the adherend surface include applying a predetermined coating solution to the adherend surface, spraying the coating solution, or immersing the adherend surface in the coating solution. Then, after forming a liquid film, a method of forming a dry film is included. The method for forming the liquid film on the adherend surface is not particularly limited, but it is preferable to cover the adherend surface without unevenness to obtain a liquid film having a uniform thickness as much as possible. What is necessary is just to form a liquid film in the to-be-adhered surface at least among the surfaces of a base material.

  The predetermined coating liquid is a mixed liquid in which a solvent and a photopolymerization initiator are mixed. The photopolymerization initiator contained in the coating liquid is not particularly limited and may be appropriately selected. Specific examples include benzophenone and riboflavin. When the manufactured complex is applied to a biomaterial such as an artificial joint, a non-toxic or physiologically safe photopolymerization initiator such as riboflavin, nicotinamide (vitamin B3), thioxanthone, etc. Is preferably selected.

  The solvent contained in the coating liquid can be appropriately selected according to the type of the photopolymerization initiator used, but is preferably a good solvent for the additive. A good solvent means a solvent having high solubility of an additive which is a solute. Specific examples of the solvent include acetone and methanol. If a solvent having a low boiling point or a solvent having high volatility is used, the solvent can be easily removed when the liquid film is dried.

  In order to form a liquid film having a uniform film thickness, it is preferable to adjust the amount of the solvent to prepare a coating liquid having a concentration that can be easily applied. In addition, depending on the solvent, the base material may be dissolved. Therefore, the solvent species and the like are appropriately selected in consideration of the solubility of the solvent with respect to the material of the base material.

  The coating liquid may contain a water-insoluble polymer. Thus, if a photoinitiator and a water-insoluble polymer are used together, a photoinitiator can be efficiently and effectively arranged on the adherend surface. The water-insoluble polymer is preferably dissolved in the solvent used for the coating solution. Specifically, polyvinyl acetate having high solubility in an organic solvent or alcohol is preferable.

  The adherend surface covered with the liquid film of the coating solution is dried. By drying, the solvent in the liquid film evaporates to form a film. By covering the adherend surface with such a film, the photopolymerization initiator is disposed on the adherend surface. Although the liquid film solution is removed by drying, the amount of the photopolymerization initiator disposed on the adherend surface does not change. Examples of means for drying the liquid film include, but are not limited to, a blower and a heater for supplying dry air whose temperature is adjusted toward the film. As described above, when a highly volatile solvent is used for the coating liquid, only the solvent can be easily removed from the liquid film only by leaving the liquid film under normal temperature and pressure.

  The operation from the formation of the coating liquid film to the formation of a dry film is preferably performed in an environment where light in the ultraviolet region is blocked. Thereby, work can be advanced without impairing the characteristics of the photopolymerization initiator.

  In the step (3), the first molded product is overlaid on the surface of the film containing the photopolymerization initiator. At this time, it is preferable that the first molded product and the surface of the film are brought into close contact with each other. In order to increase the degree of adhesion between the first molded product and the surface of the film, the structure including the first molded product and the polymer substrate is sandwiched by a glass substrate that transmits light, and a load is applied from both sides of the structure. It's fine.

  Next, light is irradiated to the 1st molded object piled up on the polymer base material. What is necessary is just to select the wavelength of the light to irradiate according to a photoinitiator (polymerization initiator etc. which are contained in the film | membrane formed in the polymer base material). Considering safety during use, ultraviolet rays are preferable. By irradiation with light, the monomer impregnated in the first molded product is polymerized into a polymer. As a result, the first molded product becomes a polymer gel having an IPN structure in which a newly formed polymer and a crosslinked polymer are entangled. In addition, a part of the newly formed polymer enters the second molded product. This polymer serves as a bridge, and the first molded product and the second molded product are bonded. Therefore, the polymer base material and polymer gel of the manufactured composite can be bonded with very high strength.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples of the present invention. The example shown here is an example of the present invention and does not limit the scope of the present invention.

[Example 1]
Preparation of first molding 2-acrylamido-2-methylpropanesulfonic acid (AMPS, 20.725 g), methylenebisacrylamide (MBAA, 0.617 g), 2-oxoglutaric acid (2-OGA, 0.014 g) and An AMPS solution consisting of water was prepared. Specifically, various raw materials of AMPS solution are added to a 200 ml beaker with a spoonful; these are dissolved in pure water to form a monomer aqueous solution; while bubbling with argon gas in the monomer solution (for about 1/4 second) The monomer aqueous solution was stirred for 1 hour using a Teflon (registered trademark) coded stirrer and a magnetic stirrer to obtain 100 ml of AMPS solution.

  A silicon frame (thickness 0.5 mm, length 150 mm, width 150 mm, width 10 mm) was placed on a glass plate (length 150 mm, width 150 mm), and further covered with a glass plate to prepare a polymerization vessel. Into this polymerization vessel, the AMPS solution (8 ml) was poured so as not to contain bubbles. The polymerization vessel into which the AMPS solution was injected was placed in a glove box with an argon gas atmosphere. Polymerization was carried out by irradiating the polymerization vessel in the glove box with ultraviolet rays having a wavelength of 365 nm for 15 hours. Ultraviolet rays were irradiated from a distance of about 20 cm from the glove box. As a result, a PAMPS gel having a thickness of 0.5 mm × length 100 mm × width 130 mm was obtained.

Next, a DMAAm solution consisting of dimethylacrylamide (DMAAm, 89.217 g), methylenebisacrylamide (MBAA, 0.046 g), 2-oxoglutaric acid (2-OGA, 0.043 g) and water was prepared. Specifically, various raw materials of the DMAAm solution are added to a 500 ml beaker with a spoonful; these are dissolved in pure water to form a monomer solution; while bubbling with argon gas in the monomer solution (at intervals of about 1/4 second) The monomer solution was stirred for 1 hour using a Teflon (registered trademark) -coated stirrer and a magnetic stirrer to obtain 300 ml of DMAAm solution.
A PAMPS gel using AMPS as a monomer raw material was immersed in a 3M DMAAm solution, and then cut into a size of 30 mm long × 25 mm wide to obtain a first molded product.

Preparation of second molded article A low molecular weight polyethylene substrate (LDPE substrate) having a width of 30 mm, a length of 70 mm, and a thickness of 1 m was prepared. The sufficiently cleaned LDPE substrate was immersed in a coating solution described later for a fixed time (10 minutes). The LDPE substrate was removed from the coating solution and dried in air using a dryer. In this way, an LDPE base material whose surface was coated with a dry film was produced to obtain a second molded product.

A predetermined amount of benzophenone and polyvinyl acetate were added to a petri dish with a coating liquid of φ150 mm, and acetone was further added to make a total amount of 100 g. A coating solution was prepared by completely dissolving benzophenone and polyvinyl acetate. The compounding amount of polyvinyl acetate was 6 parts by weight with respect to 100 parts by weight of the coating liquid. The concentrations of benzophenone were 0.2 wt%, 0.5 wt%, and 1.0 wt%, and three types of coating solutions were prepared.

Production of Composite A PAMPS gel (first molding) in a state of equilibrium swelling with a DMAAm solution was placed on the central portion of the LDPE substrate as the second molding. Both sides were sandwiched between glass plates and fixed with clips.

  The laminate of the first molded product and the second molded product sandwiched between glass plates was placed in a glove box in a nitrogen gas atmosphere. Photopolymerization was performed by irradiating the laminate in the glove box with ultraviolet rays (wavelength 365 nm) for 15 hours. Thereby, the DMAAm impregnated in the first molded product is polymerized. The polymer of DMAAm was entangled with the PAMPS gel to form a polymer gel having an IPN structure, and a composite was obtained.

Measurement of Adhesive Strength The resulting composite was immersed in water for 1 day to equilibrate and swell the polymer gel. The equilibrium swollen polymer gel was peeled off from the LDPE substrate only with one end of the bonded portion. Specifically, only about 1 cm of the adhesive width of 3 cm was peeled from the end toward the inside.

  The measurement of the adhesive strength was performed using the apparatus shown in FIG. First, the composite body which peeled off the edge part of the adhesion part was attached to the predetermined position of the T-shaped jig 24. At this time, the width direction of the composite and the width direction of the scraper 26 were made substantially parallel. Further, as shown in FIG. 3, the scraper 26 has an acute angle with a tip angle θ of 10 °, a width L1 of 42 mm, a thickness t1 of 1.7 mm, and a tip blade thickness t2 of 0.3 mm. I used something.

  Subsequently, as shown in FIG. 2B, the tip of the scraper 26 was pressed to such an extent that the portion where the polymer gel and the substrate were peeled off was touched lightly. And the polymer gel was peeled from the polyethylene base material with the scraper 26 by lowering the moving stand 21 gradually. The descending speed of the movable table 21 at this time was 10 mm / min.

  The pressing force from when the moving table 21 started to descend (start of pressing) until all of the polymer gel was peeled off from the LDPE substrate was measured. And among the measured pressing force, the average value of the maximum value m1 and the minimum value m2 was made into adhesive strength.

  The measured adhesive strength is 0.2 N / cm when using a coating solution having a benzophenone concentration of 0.2% by weight; 0.8 N / cm when using 0.5% by weight; 1.0% by weight In this case, it was 2.5 N / cm. From these results, it was confirmed that the adhesive strength was appropriately adjusted depending on the concentration of the photopolymerization initiator. It can be seen that as the concentration of benzophenone increases, the adhesive strength of the composite increases. However, if the concentration of benzophenone is excessively high, the adhesive strength may decrease. Of course, it can also be set to a stronger adhesive strength.

[Example 2]
Preparation of first molded product A PAMPS gel was prepared in the same manner as in Example 1.

  A DMAAm solution was prepared. The DMAAm solution is a mixed solution containing DMAAm as a monomer, MBAA (0.1 mol%) as a crosslinking agent, and 2-OGA (0.1 mol%) as a photopolymerization initiator. The aforementioned PAMPS gel was immersed in the DMAAm solution for 24 hours to obtain a first molded product.

Coating liquid Two kinds of coating liquids a and b were prepared using two kinds of photopolymerization initiators (polyvinyl acetate and benzophenone). The coating liquid a is a coating liquid in which the blending amount of polyvinyl acetate is adjusted, and the concentration of polyvinyl acetate is 3 types of 2%, 6%, and 10% by weight (the concentration of benzophenone is 1.0% by weight). The coating liquid b is a coating liquid in which the blending amount of benzophenone is adjusted, and the concentration of benzophenone is 0.1% by weight, 0.3% by weight, 0.5% by weight, and 1.0% by weight. (The concentration of polyvinyl acetate was constant at 6% by weight).

  In each of the coating liquid a and the coating liquid b, an LDPE substrate (length 30 mm × width 70 mm, thickness 1 mm) was immersed for a predetermined time (10 minutes) and dried in air. In this way, an LDPE substrate whose surface was coated with a dry film was produced to obtain a second molded product.

Preparation of Composite A PAMPS gel (first molded product) impregnated with a DMAAm solution was placed on an LDPE substrate coated with a film of each coating solution. The composite was formed by irradiating ultraviolet rays (wavelength 365 nm) to polymerize the monomer impregnated in the first molded product and bonding the polymer gel and the PDEL substrate.

Evaluation of Adhesive Strength The adhesive strength of each composite obtained was measured by the following method. Each composite was immersed in water to swell the polymer gel. The adhesion between the swollen polymer gel and the LDPE substrate was visually observed. The degree of peeling between the polymer gel and the LDPE substrate was judged according to the following criteria, and the adhesive strength of the composite was evaluated in three stages.
A case where the polymer gel and the LDPE base material are bonded without being peeled after the polymer gel is hydrated; ○; after the polymer gel is hydrated and swelled, A case where the LDPE base material is partially peeled: Δ: A case where the polymer gel and the LDPE base material are completely peeled after being hydrated to obtain a swollen state is indicated as x.

  Table 1 shows the adhesive strength of the composite prepared using the coating liquid (coating liquid a) with the adjusted polyvinyl acetate concentration; manufactured with the coating liquid (coating liquid b) with the adjusted benzophenone concentration Table 2 shows the adhesive strength of the resulting composite.

  As shown in Table 1, regardless of the concentration of the water-insoluble polymer (polyvinyl acetate), which is a component of the coating liquid, the polymer gel and the polymer substrate can be adhered, and the polymer gel swells. It turns out that it cannot be removed. It was confirmed that the higher the concentration of polyvinyl acetate, the slightly harder the coating solution was dried, and the reduction in film unevenness due to the coating solution.

  Further, as shown in Table 2, it can be seen that the degree of adhesion between the polymer gel and the polymer substrate can be controlled by the concentration of the photopolymerization initiator (benzophenone) which is one component of the coating liquid. That is, it was confirmed that the higher the concentration of the photopolymerization initiator in the coating solution, the higher the adhesive strength of the composite.

[Example 3]
Preparation of first molded product A PAMPS gel was prepared in the same manner as in Example 1.

  As the monomer solution, the same AAm solution and DMAAm solution as in Example 2 were prepared. The above-mentioned PAMPS gel was immersed in an AAm solution or DMAA solution for a predetermined time (24 hours), and the PAMPS gel was impregnated with the monomer solution to obtain a first molded product.

Preparation of Second Molded Article The surface of the LDPE substrate was immersed in a coating solution (acetone solution containing 6% by weight of polyvinyl acetate and 0.5% by weight of benzophenone) for a certain period of time (10 minutes) in the air. Dried. In this way, an LDPE substrate whose surface was coated with a dry film was produced to obtain a second molded product.

Production of Composite A first molded product and an LDPE substrate (second molded product) coated with a film were bonded together. This was irradiated with ultraviolet rays (wavelength 365 nm) for 16 hours to obtain a composite in which the polymer gel and the polymer substrate were adhered.

  The adhesive strength of each obtained composite was evaluated in the same manner as in Example 2. As a result, no separation was confirmed between the polymer gel containing water and the equilibrium swelling, and the polymer substrate, suggesting a very high adhesive strength.

[Example 4]
Preparation of First Molded Product In the same manner as in Example 1, a sheet-like PAMPS gel (length 130 mm × width 130 mm) was prepared, immersed in a DMAAm solution and balanced and swollen in the same manner as in Example 1, and then length 15 mm. X Cut to a width of 130 mm to obtain a first molded product.

Preparation of Second Molded Product Two LDPE base materials having a thickness of 1 mm and cut into a length of 100 mm and a width of 130 mm were prepared. The LDPE substrate was placed in acetone and stirred while boiling at 50 ° C. to wash the LDPE substrate and air dried.

  As a coating solution, an acetone solution containing a polymerization initiator and polyvinyl acetate was prepared. Two kinds of coating liquids (0.5 wt% and 0.3 wt%) having different concentrations of benzophenone as a polymerization initiator were prepared (the concentration of polyvinyl acetate was 6 wt%). The LDPE substrate was immersed in each coating solution for a fixed time (10 minutes) and dried in the air with a dryer. In this way, LDPE base materials (two sheets) coated with a film whose surface was dried were produced as a second molded product.

Production of Composite The first molded product, which was a PAMPS gel impregnated with a monomer solution, was placed on the end of one of the two LDPE substrates that were the second molded product. Furthermore, another LDPE substrate was put on the first molded product. Only the end portion of one LDPE substrate and the end portion of the other LDPE substrate overlap each other, and the first molded product is sandwiched between the overlapping portions.

  Two LDPE substrates sandwiching the first molded product were sandwiched between two glass plates. The two glass plates were fixed with clips, and pressure was applied to the extent that the gel-like substance was not destroyed, so that the LDPE substrate and the gel-like substance were brought into close contact with each other. At this time, a silicon rubber sheet having an appropriate thickness was used as a spacer so that the glass plate was not distorted.

  The stacked body sandwiched between two glass plates was placed in a glove box under a nitrogen gas atmosphere. The laminated body in the glove box was irradiated with ultraviolet rays of 365 nm for 15 hours to polymerize the monomer impregnated in the first molded product. The clip was released after ultraviolet irradiation for a predetermined time (15 hours). Two LDPE base materials were immersed in pure water and allowed to contain water, thereby removing unreacted monomers of the polymer gel to obtain a composite.

[Example 5]
Preparation of first molded product A PAMPS gel was prepared in the same manner as in Example 1. However, the ultraviolet irradiation time was 6 hours.

  A DMAAm solution consisting of DMAAm (89.217 g), MBAA (0.046 g), 2-OGA (0.043 g) and water was prepared. Specifically, in a 500 ml beaker, various raw materials of the DMAAm solution are added with a spoonful; these are dissolved in pure water to form a monomer aqueous solution; while the monomer solution is bubbled with argon gas (for about 1/4 second) The monomer solution was stirred for 1 hour using a Teflon-coded stir bar and a magnetic stirrer to obtain 300 ml of DMAAm solution.

  The PAMPS gel (thickness 0.5 mm × length 100 mm × width 130 mm) was cut with a razor to obtain a size of length 40 mm × width 60 mm. The cut gel piece was immersed in a DMAAm solution stored in a polypropylene container having a length of 150 mm, a width of 200 mm, and a depth of 55 mm, and allowed to stand for 15 hours. Thereafter, the gel piece in the glove box in an argon gas atmosphere was irradiated with ultraviolet rays having a wavelength of 365 nm for 6 hours to polymerize the DMAAm impregnated in the gel piece. Ultraviolet rays were irradiated from a position about 20 cm away from the glove box. As a result, a gel-like substance having an IPN structure in which PDMAAm was entangled with the crosslinked structure of PAMPS was obtained. The size of the obtained gel-like substance was 1 mm thick × 80 mm long × 120 mm wide.

  A cut piece having a length of 50 mm and a width of 50 mm was cut out from the obtained gel-like substance. The cut piece was immersed in the DMAAm solution stored in a polypropylene container having a length of 150 mm, a width of 200 mm, and a depth of 55 mm, and left for 6 hours. As a result, a first molded article impregnated with the DMAAm solution was obtained.

Preparation of Second Molded Article A polyethylene substrate having a thickness of 1 mm × length 70 mm × width 70 mm was prepared. In an environment shielded from light with aluminum foil, the polyethylene substrate was put into the following coating solution using tweezers and allowed to stand for 10 minutes. The polyethylene substrate was taken out from the coating liquid and dried in the air to obtain a polyethylene substrate coated with a film containing a photopolymerization initiator, which was used as a second molded product.

Coating liquid To a petri dish with a diameter of 150 mm, 0.3 g of benzophenone was added using a spatula; 2.0 g of polyvinyl acetate was added using a spoon. Methanol was added to these and stirred with a glass rod to prepare a solution of 100 g as a solution.

Production of Composite A composite was formed using the first molded product and the second molded product. First, the 2nd molding was put on the glass plate, and also the 1st molding was put on it. A glass substrate was further placed on the first molded product to obtain a laminate. The obtained laminate was placed in a glove box with an argon gas atmosphere. The laminate in the glove box was irradiated with ultraviolet rays having a wavelength of 365 nm for 6 hours from a position approximately 20 cm away to polymerize the monomer. Thereby, the polyethylene base material and the polymer gel (formed by polymerization of the monomer of the first molded product) were adhered to produce a composite. The polymer gel constituting the composite is an IPN gel in which a PAMPS having a crosslinked structure and an IPN gel composed of PDMAAm having a crosslinked structure are further entangled with a crosslinked polymer composed of PDMAAm.

  The obtained composite is immersed in water, the polymer gel is hydrated to obtain an equilibrium swelling, and then the equilibrium swelling of the polymer gel and the polymer substrate are manually peeled off to evaluate the adhesive strength of the composite. did. As a result, it was confirmed that the polymer gel and the polymer substrate were firmly bonded to such an extent that the polymer gel was likely to break depending on the force.

[Example 6]
A composite was produced in the same manner as in Example 5 except that the first molded product was changed.
A cut piece cut out from a PAMPS gel to a size of 50 mm long × 50 mm wide was immersed in a DMAAm solution (300 ml) stored in a polypropylene container 150 mm long × 200 mm wide × 55 mm deep and left for 15 hours. A PAMPS gel impregnated with the DMAAm solution was used as the first molded product.
A composite was produced in the same manner as in Example 5 using the obtained first molded product. The polymer gel composing the prepared composite has an IPN structure in which a crosslinked polymer made of PDMAAm is entangled with a crosslinked structure of a crosslinked polymer PAMPS.

  After immersing the finished composite in water and imbibing the polymer gel to equilibrate swelling, the adhesive strength of the composite is evaluated by manually peeling the polymer gel and the polymer substrate that have undergone equilibrium swelling. did. As a result, it was confirmed that the polymer gel and the polymer substrate were firmly bonded to such an extent that the polymer gel was likely to break depending on the force.

[Example 7]
A composite was produced in the same manner as in Example 5 except that a sheet-like polypropylene substrate was used as the second molded product. The size of the polypropylene substrate is the same as in Example 5. The polymer gel constituting the composite of Example 7 has an IPN structure in which a crosslinked polymer composed of PDMAAm is entangled with the crosslinked structure of the crosslinked polymer PAMPS.

  After immersing the finished composite in water and imbibing the polymer gel to equilibrate swelling, the adhesive strength of the composite is evaluated by manually peeling the polymer gel and the polymer substrate that have undergone equilibrium swelling. did. As a result, it was confirmed that the polymer gel and the polymer substrate were firmly bonded to such an extent that the polymer gel was likely to break depending on the force.

[Example 8]
A composite was produced in the same manner as in Example 5 except that a sheet-like polystyrene substrate was used as the second molded product. The size of the polystyrene substrate is the same as in Example 5. The polymer gel constituting the composite of Example 8 has an IPN structure in which a crosslinked polymer made of PDMAAm is entangled with the crosslinked structure of the crosslinked polymer PAMPS.

  The obtained composite was immersed in water, and the polymer gel was hydrated to achieve equilibrium swelling. The adhesive strength of the composite was evaluated by manually peeling the polymer gel and the polymer substrate that had been subjected to equilibrium swelling. As a result, it was confirmed that the polymer gel and the polymer substrate were firmly bonded to such an extent that the polymer gel was likely to break depending on the force.

[Example 9]
Preparation of first molded product An aqueous solution of polyvinyl alcohol (PVA) was prepared. Specifically, 90 ml of cold water of about 5 ° C. is placed in a 100 ml glass beaker; 10 g of PVA powder having a polymerization degree of 2000 is dispersed; this PVA dispersion is heated in a hot water bath (water temperature 100 ° C.) to It was completely dissolved to obtain a 10 wt% PVA aqueous solution.

  The PVA aqueous solution (10 ml) was poured into a container having a smooth bottom surface and a diameter of 20 mm and a height of 30 mm so that no bubbles would enter. The container into which the PVA aqueous solution was poured was put in a freezer at −20 ° C. and allowed to stand for 2 hours or more. After confirming that the PVA aqueous solution was completely frozen, it was thawed at room temperature. This freeze-thaw step was repeated a total of 5 times. As a result, an elastic polymer gel (PVA freeze-thaw gel) was obtained.

  Next, an AAm solution containing MBA (0.1 mol%) as a crosslinking agent and 2-OGA (0.1 mol%) as a photopolymerization initiator was prepared in AAm as a monomer. The PVA freeze-thaw gel was immersed in the AAm solution for 24 hours to obtain a first molded product.

Preparation of Second Molded Article The surface of the LDPE substrate was immersed in a coating solution (acetone solution containing 6% by weight of polyvinyl acetate and 0.5% by weight of benzophenone) for a certain period of time (10 minutes) in the air. Dried. In this way, an LDPE substrate whose surface was coated with a dry film was produced to obtain a second molded product.

Production of Composite A first molded product and an LDPE substrate (second molded product) coated with a film were bonded together. This was irradiated with ultraviolet rays having a wavelength of 365 nm for 16 hours to obtain a composite in which a polymer gel (PVA freeze-thaw gel) and a polymer (LDPE) substrate were bonded.

[Comparative Example 1]
A PAMPS gel was prepared from an AMPS monomer and an AMPS solution containing MBAA (4 mol%) and 2-OGA (0.1 mol%) by the same method as in Example 1. The PAMPS gel is a polymer gel having a crosslinked structure. On the other hand, the surface of the polyethylene substrate was coated with the coating solution used in Example 3.
A PAMPS gel was overlaid on a polyethylene substrate coated with a coating solution. The sample was obtained by irradiating with ultraviolet rays.

  The obtained sample was immersed in water and equilibrated and swollen by allowing the PAMPS gel to contain water. The swollen PAMPS gel was adhered to the polyethylene substrate, but was destroyed by the swelling pressure. A manual peeling test could not be performed.

  INDUSTRIAL APPLICABILITY The present invention is useful for members made by taking advantage of the properties of polymer gels such as elasticity, deformability, impact absorption, surface friction characteristics, substance permeability, and external stimulus responsiveness. The composite material of the polymer gel and the support obtained by the present invention can be widely used from the industrial field to the medical field. For example, in the industrial field, it is expected that the joint part of a robot will be applied as a new shock absorbing joint having both low friction and cushioning properties, and oil-free non-metallic bearings. On the other hand, in the medical field, application to all biomaterials including cartilage of artificial joints, artificial organs, artificial vocal cords, and artificial blood vessels is expected. In addition, when an engineering plastic having excellent heat resistance is used as a support, a polymer gel can be bonded and fixed to the support, so that it can be used, for example, as a vibration absorber that absorbs vibrations of an engine or a motor.

It is sectional drawing of an example of the polymer gel composite_body | complex which concerns on this invention. It is the schematic of an example of the apparatus which measures the adhesive strength of the polymer gel which concerns on this invention. It is the schematic of an example of the scraper used for the apparatus which measures adhesive strength.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Polymer gel composite body 11 Base material 12 Polymer gel 14 Polymerization layer 20 Adhesive strength measuring apparatus 26 Scraper

Claims (8)

A plastic substrate ;
An IPN structure comprising a polymer gel impregnated with a liquid adhered to the plastic substrate , the polymer chain having a crosslinked structure, and a polymer chain having a crosslinked structure or a non-crosslinked structure independent of the polymer chain A polymer gel having
A water-insoluble polymer disposed between the polymer substrate and the polymer gel and capable of holding a polymerization initiator ,
The polymer gel composite whose adhesive strength B of the said plastic base material and the said polymer gel measured by the following method is 0.1 N / cm-25 N / cm .
[Measurement method of adhesive strength B]
The polymer gel contained in the polymer gel composite is hydrated to achieve equilibrium swelling;
Peeling off the end of the bonded portion between the equilibrium swollen polymer gel and the plastic substrate;
Inserting a stripping member having an acute angle (10 °) into the gap between the polymer gel at the peeled end and the plastic substrate;
By pressing the stripping member against the site where the equilibrium swollen polymer gel and the plastic substrate are peeled off, all of the polymer gel is stripped from the plastic substrate, and the pressing of the stripping member is started. To measure the pressing force until all of the polymer gel is peeled off from the plastic substrate;
The result of calculation using the following equation (2) from the average value M (N) of the maximum value and the minimum value of the measured pressing force is defined as adhesive strength B.
Adhesive strength B (N / cm) = M × tan 10 ° / L (2)
However, M is an average pressing force value (N), and L is a width (cm) of the peeled adhesive portion . The polymer gel composite according to claim 1 , wherein an adhesive strength A between the plastic substrate and the polymer gel, measured by the following method, is 0.5 N / cm to 50 N / cm .
[Measurement method of adhesive strength A]
Peeling off the end of the adhesive portion between the polymer gel contained in the polymer gel composite in the atmospheric environment and the plastic substrate;
Inserting a stripping member having an acute angle (10 °) into the gap between the polymer gel at the peeled end and the plastic substrate;
By pressing the stripping member against the site where the polymer gel and the plastic substrate have been peeled off, all of the polymer gel is peeled off from the plastic substrate, and from the start of pressing the stripping member, Measuring the pressing force until all of the molecular gel is removed from the plastic substrate;
The result of calculation using the following formula (1) from the average value M (N) of the maximum value and the minimum value of the measured pressing force is defined as adhesive strength A.
Adhesive strength A (N / cm) = M × tan 10 ° / L (1)
However, M is an average pressing force value (N), and L is a width (cm) of the peeled adhesive portion . The polymer gel composite according to claim 1, wherein a part of the polymer chain having a crosslinked structure or a non-crosslinked structure independent of the polymer chain has penetrated into the plastic substrate. The polymer gel composite according to any one of claims 1 to 3 , wherein the liquid impregnated in the polymer gel is water . The polymer gel composite according to claim 4 , wherein the water content of the polymer gel is 10 wt% to 99 wt%. The polymer gel composite according to any one of claims 1 to 3, wherein the liquid impregnated in the polymer gel is a non-volatile liquid . A plastic substrate, is bonded to the plastic substrate, a polymer gel having an IPN structure impregnating liquid, water can hold the placed polymerization initiator between the polymer gel and the plastic substrate A method for producing a polymer gel composite comprising an insoluble polymer ,
Preparing a first molded article comprising a crosslinked polymer impregnated with a monomer, a polymerization initiator and a liquid, and optionally a crosslinking agent;
At least part of the surface is a step to prepare a plastic substrate covered with a film of water-insoluble polymer containing a photopolymerization initiator, and the photopolymerization initiator of the first superimposed on the film of the water-insoluble polymer comprising A method for producing a polymer gel composite, comprising a step of irradiating a molded product with light. The manufacturing method according to claim 7 , wherein the monomer is a non-electrolyte.

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