Adhesive composition

Abstract

To provide an adhesive composition that enables enhancement of adhesive strength to soft tissue with a short curing time while maintaining flexibility of an adhesion surface.SOLUTION: The adhesive composition comprises (A) a polymer compound having a repeating unit represented by general formula (1) [in which R1 indicates an oxygen atom or a bonding hand, R2 indicates a hydrogen atom or a hydroxyl group, and * indicates a repeating site] and having a repeating unit represented by general formula (2): *-(CH(OH)-CH2)-*, (B) a water-soluble polyphenol, and (C) a salt of at least one metal selected from the group consisting of alkaline earth metals, transition metals belonging to the 4th period of the periodic table, and aluminum.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an adhesive composition. [Background technology]

[0002] An adhesive is a substance used to attach the surface of one object to another. The International Organization for Standardization (ISO) defines it as follows: "Adhesion is the state in which two surfaces are held together by chemical or physical forces, or both. An adhesive is a substance that makes it possible to join two or more objects together by adhesion."

[0003] Due to their convenience, adhesives are widely used in various fields in daily life and industrial activities. Among the adhesives that are commonly used for medical purposes are cyanoacrylate adhesives and fibrin adhesives.

[0004] Of these, cyanoacrylate adhesives are characterized by their high adhesive strength, but they harden the adhesive surface between living bodies. As a result, when the entire body moves, such as during exercise, the adhesive surface becomes difficult to move, increasing the load, and they cannot be used in areas where movement of soft tissues (skin, blood vessels, muscles, internal organs, etc.) is required.

[0005] On the other hand, in contrast to cyanoacrylate adhesives, fibrin adhesives have flexibility of the adhesive surface, but have low adhesive strength and are difficult to harden in a short time.

[0006] If there were a medical adhesive with high adhesive strength and excellent short-term curing properties, it would be possible to shorten the time required to close an incision during surgery, thereby shortening the total time of surgery. Although such an adhesive would be expected to reduce the burden on patients, it has not yet been discovered.

[0007] For this reason, there has been a demand for medical adhesives that have excellent adhesive strength and can be cured in a short time.

[0008] In contrast, Patent Document 1 shows that by containing a polyvinyl alcohol compound, a water-soluble polyphenol compound, and water, the adhesive is virtually insoluble in water, and can be used for adhesion in both underwater and non-underwater environments without a curing process, and can be used as a medical adhesive. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] International Publication No. 2019 / 039858 Summary of the Invention [Problem to be solved by the invention]

[0010] However, Patent Document 1 does not describe the adhesive strength of soft tissue, and there is a problem in that sufficient adhesive strength cannot be obtained.

[0011] The present invention is intended to solve the above-mentioned problems, and aims to provide an adhesive composition that can increase adhesive strength to soft tissue in a short curing time while maintaining the flexibility of the adhesive surface. [Means for solving the problem]

[0012]

[0006] In view of the above problems, the present inventors have conducted extensive research and found that by adding a polyvinyl alcohol compound having a specific phosphate group introduced therein, a water-soluble polyphenol compound, and a specific salt, it is possible to provide an adhesive composition that can increase adhesive strength in a short curing time while maintaining the flexibility of the adhesive surface. The present invention was completed based on this finding. Specifically, the present invention includes the following features.

[0013] Section 1. (A) General formula (1):

[0014] [ka] [In the formula, R 1 indicates an oxygen atom or a bond. 2 indicates a hydrogen atom or a hydroxyl group. * indicates a repeating portion.] A repeating unit represented by the formula: General formula (2):

[0015] [ka] A polymer compound having a repeating unit represented by the formula: (B) water-soluble polyphenols, and (C) a salt of at least one metal selected from the group consisting of alkaline earth metals, transition metals belonging to the fourth period of the periodic table, and aluminum An adhesive composition comprising:

[0016] Item 2. The repeating unit represented by general formula (1) contained in the polymer compound (A) is represented by general formulas (1A), (1B), and (1C):

[0017] [ka] Item 2. The adhesive composition according to item 1, comprising at least one repeating unit selected from the group consisting of:

[0018] Item 3. The repeating unit represented by general formula (1) contained in the polymer compound (A) is represented by general formula (1A):

[0019] [ka] Item 3. The adhesive composition according to item 1 or 2, containing a repeating unit represented by the following formula:

[0020] Item 4. The adhesive composition according to any one of Items 1 to 3, wherein the polymer compound (A) contains 3 to 60 mol % of repeating units represented by general formula (1), where the total amount of repeating units represented by general formula (1) and repeating units represented by general formula (2) is 100 mol %.

[0021] Item 5. The adhesive composition according to any one of Items 1 to 4, wherein the water-soluble polyphenol compound (B) is at least one selected from the group consisting of hydroxybenzoic acid compounds, hydroxycinnamic acid compounds, flavonoid compounds, stilbene compounds, caffeic acid, chlorogenic acid, pyrogallol, gallic acid, catechin, hydrolyzable tannins, condensed tannins, and 3-theaflavin gallate.

[0022] Item 6. The adhesive composition according to any one of Items 1 to 5, wherein the content of the water-soluble polyphenol compound (B) is 10 to 1000 parts by mass per 100 parts by mass of the polymer compound (A).

[0023] Item 7. The adhesive composition according to any one of Items 1 to 6, wherein the salt (C) is a salt of at least one metal selected from the group consisting of Fe, Zn, Mn, Cu, Ca, Mg, Al, Sr, and Ba.

[0024] Item 8. The adhesive composition according to any one of Items 1 to 7, wherein the salt (C) is a chloride.

[0025] Item 9. The adhesive composition according to any one of Items 1 to 8, wherein the salt (C) is a chloride of calcium.

[0026] Item 10. The adhesive composition according to any one of Items 1 to 9, wherein the content of the salt (C) is 10 to 1000 parts by mass per 100 parts by mass of the polymer compound (A).

[0027] Item 11. The adhesive composition according to any one of Items 1 to 10, which is a solid adhesive.

[0028] Item 12. The adhesive composition according to any one of Items 1 to 11, which is in the form of a sheet.

[0029] Item 13. The adhesive composition according to any one of Items 1 to 12, which is a medical adhesive. [Effects of the Invention]

[0030] According to the present invention, an adhesive composition can be provided that can increase adhesive strength to soft tissue in a short curing time while maintaining flexibility of the adhesive surface. Such an adhesive composition is useful as a medical adhesive. [Brief explanation of the drawings]

[0031] [Figure 1] The results of the adhesive strength of the test pieces for adhesion tests (curing time: 10 minutes) obtained in Examples 1 to 7 and Comparative Examples 1 to 5 are shown. DETAILED DESCRIPTION OF THE INVENTION

[0032] The present invention will be described in detail below.

[0033] In this specification, the term "containing" is a concept that encompasses all of "comprise," "consist essentially of," and "consist only of."

[0034] In addition, in this specification, the expression "A to B" means "A or more and B or less."

[0035] 1. Adhesive composition The adhesive composition of the present invention comprises (A) a compound represented by the general formula (1):

[0036] [ka] [In the formula, R 1 indicates an oxygen atom or a bond. 2indicates a hydrogen atom or a hydroxyl group. * indicates a repeating portion.] A repeating unit represented by the formula: General formula (2):

[0037] [ka] A polymer compound having a repeating unit represented by the formula: (B) water-soluble polyphenols, and (C) a salt of at least one metal selected from the group consisting of alkaline earth metals, transition metals belonging to the fourth period of the periodic table, and aluminum Contains:

[0038] By adopting such a constitution, the adhesive composition of the present invention can be obtained as a solid (particularly a gel-like solid, a sheet-like solid, a powder, etc.) due to the presence of the salt (C), and therefore has excellent handleability.

[0039] Furthermore, the adhesive composition of the present invention uses a combination of a polymer compound (A) having a specific phosphate group introduced therein, a water-soluble polyphenol compound (B), and a salt (C), so that the adhesive surface between soft tissues is flexible and it is possible to obtain sufficiently high adhesive strength even with a short curing time.

[0040] (1-1) Polymer compound (A) The adhesive composition of the present invention has the following general formula (1):

[0041] [ka] [In the formula, R 1 indicates an oxygen atom or a bond. 2 indicates a hydrogen atom or a hydroxyl group. * indicates a repeating portion.] A repeating unit represented by the formula: General formula (2):

[0042] [ka] The polymer compound contains a repeating unit represented by the formula:

[0043] In general formula (1), R 1 represents an oxygen atom or a bond, and among these, an oxygen atom is preferred.

[0044] In general formula (1), R 2 represents a hydrogen atom or a hydroxyl group. Among these, a hydroxyl group is preferred from the viewpoints of flexibility of the adhesive surface, adhesive strength after short curing time, etc.

[0045] From the above, examples of the repeating unit represented by general formula (1) include those represented by general formulas (1A), (1B), (1C), etc.:

[0046] [ka] Among them, repeating units represented by general formula (1A):

[0047] [ka] A repeating unit represented by the following formula is preferred.

[0048] The polymer compound (A) may contain one or more of these repeating units represented by general formula (1). The polymer compound (A) preferably contains 50 to 100 mol % of repeating units represented by general formula (1A), and preferably contains 0 to 50 mol % of the total amount of repeating units represented by general formula (1B) and general formula (1C), where the total amount of repeating units represented by general formula (1) is 100 mol %.

[0049] The polymer compound (A) contains a repeating unit represented by the general formula (1) above as well as a repeating unit represented by the general formula (2):

[0050] [ka] The polymer further contains a repeating unit represented by the following formula:

[0051] From the viewpoints of flexibility of the adhesive surface, adhesive strength after short curing times, etc., the repeating units represented by general formula (1) are preferably contained in an amount of 3 to 60 mol %, more preferably 5 to 50 mol %, based on 100 mol % of the total of the repeating units represented by general formula (1) and the repeating units represented by general formula (2).Similarly, the repeating units represented by general formula (2) are preferably contained in an amount of 40 to 97 mol %, more preferably 50 to 95 mol %, based on 100 mol % of the total of the repeating units represented by general formula (1) and the repeating units represented by general formula (2).

[0052] The polymer compound (A) may contain repeating units represented by the general formulae (1) and (2) above, as well as repeating units represented by the general formula (3):

[0053] [ka] It is also possible to have a repeating unit represented by the following formula:

[0054] From the viewpoints of flexibility of the adhesive surface, adhesive strength in a short curing time, etc., the repeating unit represented by general formula (3) is preferably contained in an amount of 0 to 20 mol %, and more preferably 0 to 10 mol %, where the total amount of the repeating unit represented by general formula (1), the repeating unit represented by general formula (2), and the repeating unit represented by general formula (3) is taken as 100 mol %.

[0055] These polymer compounds (A) can be used alone or in combination of two or more.

[0056] The content of the polymer compound (A) in the adhesive composition of the present invention is not particularly limited, but from the viewpoints of flexibility of the adhesive surface, adhesive strength in a short curing time, etc., it is preferably 10 to 70 mass%, more preferably 20 to 60 mass%, where the total amount of the polymer compound (A), the water-soluble polyphenol compound (B), and the salt (C) is 100 mass%.

[0057] The method for producing the polymer compound (A) is not particularly limited, but for example, a polymer compound having a repeating unit represented by general formula (2) can be reacted with phosphoric acid, phosphorous acid, or the like in a solvent.

[0058] The amount of phosphoric acid, phosphorous acid, etc. used is not particularly limited and may vary depending on the content of the repeating unit represented by general formula (1) in the polymer compound (A) to be obtained, but can be, for example, 100 to 500 parts by mass per 100 parts by mass of the polymer compound having the repeating unit represented by general formula (2).

[0059] In addition to the above, the polymer compound (A) can be produced by a method of combining a polymer compound having a repeating unit represented by general formula (2) with a polymer compound having a repeating unit represented by general formula (4):

[0060] [ka] [In the formula, R 3 are the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. X 1 indicates a halogen atom.] and a compound represented by general formula (5): R 4 -X 2 (5) [In the formula, R 4 represents a linear or branched alkyl group having 1 to 4 carbon atoms. 2 indicates a halogen atom.] The compound represented by the formula (I) can also be produced by further adding a compound represented by the formula (I) and heating the compound at a temperature of, for example, 100°C or higher to cause the Arbuzov reaction, and then adding water to carry out a hydrolysis reaction.

[0061] The amounts of the various components added in this case are not particularly limited, and may be in the amounts normally used in the Arbuzov reaction.

[0062] As the solvent, for example, dimethylformamide, dimethylacetamide, dimethylsulfoxide, etc. can be used.

[0063] The reaction temperature is not particularly limited, but can be, for example, 100 to 190°C. The reaction temperature may be appropriately changed depending on the boiling point of the solvent used. The reaction time is also not particularly limited, but can be, for example, 1 to 48 hours.

[0064] After the reaction is completed, the product may be purified by a conventional method as needed (for example, the product may be dissolved in water, dimethylformamide, dimethylacetamide, dimethylsulfoxide, or the like and then reprecipitated using a poor solvent such as ethanol or acetone, the precipitate may be washed, dissolved in water, a cation exchange resin may be added, the mixture may be filtered, and the precipitate may be washed again), to obtain polymer compound (A).

[0065] (1-2) Water-soluble polyphenol compounds (B) A substance in which one hydrogen atom in a benzene ring (C6H6) is replaced with a hydroxyl group is called a phenol, and here, aromatic compounds with two or more hydroxyl groups are called water-soluble polyphenols. Many compounds with this structure exist in nature, including catechins in green tea, chlorogenic acid in coffee, and the red and purple anthocyanin pigments found in strawberries, eggplants, grapes, black beans, and adzuki beans. Polyphenol compounds are also found in a variety of other foods, including vegetables, fruits, cocoa, and red wine.

[0066] In the present invention, examples of the water-soluble polyphenol compound (B) include hydroxybenzoic acid compounds (hydroxybenzoic acid, salicylic acid, gallic acid, protocatechuic acid, vanillic acid, 3,4-dihydroxybenzoic acid, and derivatives thereof), hydroxycinnamic acid compounds (hydroxycinnamic acid, caffeic acid, ferulic acid, sinapic acid, coumaric acid, caffeoyl glucose, rosmarinic acid, ferulylquinic acid, chlorogenic acid, caftaric acid, and derivatives thereof), flavonoid compounds (flavonoids, quercetin, rutin, kaempferol, myricetin, catechin, gallocatechin, epicatechin, epigallocatechin gallate, luteolin, apigenin, morin, hesperetin, naringe Examples of water-soluble polyphenol compounds (B) include tannin, eriodictyol, hesperidin, naringin, genistein, daidzein, cyanidin, delphinidin, malvidin, pelargonidin, peonidin, petunidin, procyanidin, and derivatives thereof), stilbene compounds (stilbene, resveratrol, piceatannol, pinosylvin, pterostilbene, rhapontigenin, pterostilbene, isorhapontigenin, rhapontin, ponticin, piceid, astringin, and derivatives thereof), anthocyanins, pyrogallol, ellagic acid, hydrolyzable tannins, condensed tannins, and 3-gallic acid theaflavin. Examples of hydrolyzable tannins include tannic acid, gallotannin, and ellagitannin. These water-soluble polyphenol compounds (B) can be used alone or in combination of two or more.

[0067] The content of the water-soluble polyphenol compound (B) in the adhesive composition of the present invention is not particularly limited, but from the viewpoints of flexibility of the adhesive surface, adhesive strength in a short curing time, etc., it is preferably 10 to 70 mass%, more preferably 20 to 60 mass%, where the total amount of the polymer compound (A), the water-soluble polyphenol compound (B), and the salt (C) is 100 mass%.

[0068] The content of the water-soluble polyphenol compound (B) in the adhesive composition of the present invention is not particularly limited, but from the viewpoints of flexibility of the adhesive surface, adhesive strength in a short curing time, etc., it is preferably 10 to 1000 parts by mass, more preferably 20 to 800 parts by mass, per 100 parts by mass of the polymer compound (A).

[0069] (1-3) Salt (C) The salt (C) used in the adhesive composition of the present invention is a salt of at least one metal selected from the group consisting of alkaline earth metals, transition metals belonging to the fourth period of the periodic table, and aluminum. The use of such a salt (C) allows the adhesive composition of the present invention to be obtained as a solid (particularly a gel-like solid, a sheet-like solid, a powder, etc.), and also improves adhesive strength in a short curing time. In another embodiment, the salt (C) used in the present invention may be a salt of at least one metal selected from the group consisting of alkaline earth metals and transition metals belonging to the fourth period of the periodic table.

[0070] The alkaline earth metal in the salt (C) used in the adhesive composition of the present invention is not particularly limited, and examples thereof include Mg, Ca, Sr, and Ba.

[0071] Furthermore, examples of transition metals belonging to the fourth period of the periodic table in the salt (C) used in the adhesive composition of the present invention include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn.

[0072] Among these, from the viewpoints of the flexibility of the adhesive surface, adhesive strength in a short curing time, etc., the metal used in the salt (C) used in the adhesive composition of the present invention is preferably Fe, Zn, Mn, Cu, Ca, Mg, Al, Sr, Ba, etc., more preferably Fe, Zn, Mn, Cu, Ca, Mg, Sr, Ba, etc., even more preferably Cu, Ca, etc., and particularly preferably Ca.

[0073] Furthermore, examples of the salt (C) used in the adhesive composition of the present invention include halides (chlorides, bromides, iodides, etc.), nitrates, sulfates, etc., and from the viewpoints of flexibility of the adhesive surface, adhesive strength in a short curing time, etc., halides are preferred, and chlorides are more preferred.

[0074] Specific examples of the salt (C) that satisfies the above conditions include CaCl2, CuCl2, etc. These salts (C) can be used alone or in combination of two or more.

[0075] The content of the salt (C) in the adhesive composition of the present invention is not particularly limited, but from the viewpoints of flexibility of the adhesive surface, adhesive strength in a short curing time, etc., the content is preferably 1 to 40 mass%, more preferably 5 to 30 mass%, based on 100 mass% of the total amount of the polymer compound (A), the water-soluble polyphenol compound (B), and the salt (C).

[0076] The content of the salt (C) in the adhesive composition of the present invention is not particularly limited, but from the viewpoints of flexibility of the adhesive surface, adhesive strength in a short curing time, etc., it is preferably 10 to 1000 parts by mass, more preferably 25 to 500 parts by mass, per 100 parts by mass of the polymer compound (A).

[0077] (1-4) Adhesive composition The adhesive composition of the present invention may consist solely of the above-mentioned polymer compound (A), water-soluble polyphenol compound (B) and salt (C), or may contain other substances separately.

[0078] For example, when various solvents such as water are used in producing the adhesive composition of the present invention, the adhesive composition of the present invention can be obtained as a solid (particularly a gel-like solid, a sheet-like solid, a powder, etc.), and therefore the solvent can be removed, but this does not exclude that some of the solvent may remain. Furthermore, this does not exclude polymeric compounds other than the polymeric compound (A), such as polymeric compounds comprising repeating units other than those represented by general formulas (1), (2), and (3). However, from the viewpoints of the flexibility of the adhesive surface, adhesive strength after a short curing time, etc., the content of these other substances is preferably 0 to 10% by mass, more preferably 0.1 to 5% by mass, based on 100% by mass of the total amount of the adhesive composition of the present invention.

[0079] As described above, the adhesive composition of the present invention can be obtained as a solid (particularly a gel-like solid, a sheet-like solid, a powder, etc.), and therefore the adhesive composition of the present invention can be made into a solid adhesive. In this case, the adhesive composition of the present invention can be formed into a sheet or powder. The adhesive composition of the present invention as described above is useful, for example, as a medical adhesive, an industrial adhesive, an underwater adhesive, an underwater sealant, an adhesive putty, an adhesive tape, a moist wound healing dressing, a medical adhesion preventative, a hemostatic agent, etc.

[0080] The method for producing the adhesive composition of the present invention is not particularly limited, and various components such as the polymer compound (A), the water-soluble polyphenol compound (B), and the salt (C) can be mixed together. In this case, in order to mix them more uniformly, it is preferable to prepare the polymer compound (A), the water-soluble polyphenol compound (B), the salt (C), etc. as aqueous solutions and mix them in the liquid phase.

[0081] After mixing as described above, the mixture may be subjected to centrifugation, drying, etc., as required, to obtain the adhesive composition of the present invention in a solid form (particularly in the form of a sheet, powder, etc.).

[0082] The conditions for centrifugation are not particularly limited, but for example, centrifugation can be carried out at a rotation speed of 2,000 to 4,000 rpm for 10 to 60 minutes.

[0083] The drying conditions are not particularly limited, but can be carried out, for example, at a temperature of 0°C to 100°C for 30 minutes to 24 hours. [Example]

[0084] The present invention will be explained in more detail below by showing examples and comparative examples, but the scope of the present invention is not limited to these examples.

[0085] (Synthesis Example 1: Synthesis of phosphorylated polyvinyl alcohol compound P-PVA (1)) A 5 L reaction vessel was charged with 200 g of commercially available polyvinyl alcohol (PVA (1); degree of polymerization 1300, saponification degree 99 mol% or more) and 3843 g of dimethylformamide. The temperature was raised to 150 °C to dissolve the PVA. Then, 786 g of phosphoric acid (concentration 85% by mass, 668 g of phosphoric acid) was added, and the reaction was carried out at 150 °C for 5.5 hours to synthesize P-PVA (1). 370 g of by-product water was recovered along with dimethylformamide. After the reaction was completed, ethanol was added to precipitate P-PVA (1), which was then filtered and washed with ethanol. Next, this precipitate was dissolved in water, and acetone was added to reprecipitate P-PVA (1). The precipitate was then filtered and washed with acetone. After dissolving the P-PVA (1) in water again, a cation exchange resin was added, stirred, and filtered. The water was distilled off, and the precipitated solid was dried to obtain 235 g of a phosphorylated polyvinyl alcohol compound (P-PVA (1)). The degree of substitution of phosphate groups is 1 The content was determined to be 23 mol% by H-NMR. Therefore, it can be understood that the obtained P-PVA (1) contains 23 mol% of repeating units represented by general formula (1A). Furthermore, since the saponification degree of the raw material PVA is 99 mol% or more, it can be understood that the obtained P-PVA (1) contains 77 mol% of repeating units represented by general formula (2).

[0086] (Synthesis Example 2: Synthesis of phosphorylated polyvinyl alcohol compound P-PVA (2)) A 2 L reaction vessel was charged with 70 g of commercially available polyvinyl alcohol (PVA (1); degree of polymerization 1300, degree of saponification 99 mol% or more) and 1345 g of dimethylformamide. The temperature was raised to 150°C to dissolve the PVA. Then, 91.7 g of phosphoric acid (concentration 85% by mass, 77.9 g as phosphoric acid) was added and reacted at 150°C for 3 hours. Thereafter, the same procedure as in Synthesis Example 1 was followed to obtain 68.9 g of a phosphated polyvinyl alcohol compound (P-PVA (2)). The substitution degree of the phosphate group was 1 The repeating unit content was determined to be 7 mol% by H-NMR. Therefore, it can be understood that the obtained P-PVA (2) contains 7 mol% of the repeating unit represented by general formula (1A). Furthermore, since the saponification degree of the raw material PVA is 99 mol% or more, it can be understood that the obtained P-PVA (2) contains 93 mol% of the repeating unit represented by general formula (2).

[0087] (Example 1: Preparation of adhesive composition) <Production of Sheet-Shaped Adhesive Composition> (A) 4.1 g of a 20% by mass aqueous solution of the phosphorylated polyvinyl alcohol compound (P-PVA (1)) synthesized in Synthesis Example 1, (B) 4.1 g of a 5% by mass aqueous solution of tannic acid, and (C) 4.1 g of a 20% by mass aqueous solution of calcium chloride (CaCl2) as an additive were mixed. The mixture was centrifuged at 3000 rpm for 30 minutes to obtain a gel-like solid that had sunk to the bottom. The obtained solid was spread evenly on a Teflon (registered trademark) sheet and dried at room temperature (25°C) to obtain 0.86 g of a sheet-like adhesive composition.

[0088] <Preparation of test specimen materials> First, two test specimens were prepared using the following materials: - 2 x Stainless steel (SUS) plates (2.5cm wide x 8cm long) 2 slices of pork thigh (approximately 2mm thick, cut into 2.5cm wide x 1.6cm long pieces) - Cyanoacrylate adhesive (Aron Alpha manufactured by Toagosei Co., Ltd.).

[0089] A cyanoacrylate adhesive was applied to the edge of a stainless steel plate, which had been washed with water and then ethanol, in an area 2.5 cm wide x 1.6 cm long, and pork thigh meat was attached to the applied surface as soft tissue. Another plate was prepared in the same way, yielding a total of two test specimen materials.

[0090] <Preparation of test specimens for adhesion tests> Of the test specimen materials prepared above, 100 mg of sheet-shaped adhesive composition was attached to the surface of the pork meat of one test specimen material, and then overlapped with the pork meat of the other test specimen material. The pork was bonded together so that the stretching directions of the SUS plates were opposite each other. A 50 g weight was then placed on the bonded surface. The specimen was placed in a natural convection dryer set at 37°C and allowed to bond for 10 minutes to prepare a test specimen for the adhesion test.

[0091] Examples 2 to 5 Sheet-shaped adhesive compositions were produced in the same manner as in Example 1, except that the aqueous solution concentrations of the components were changed as shown in Table 1 below, and test pieces for adhesion tests were prepared.

[0092] Example 6 A sheet-shaped adhesive composition was produced in the same manner as in Example 1, except that P-PVA (2) obtained in Synthesis Example 2 was used instead of P-PVA (1) obtained in Synthesis Example 1, and the aqueous solution concentration of each component was changed as shown in Table 1 below, and a test piece for an adhesion test was prepared.

[0093] Example 7 A sheet-shaped adhesive composition was produced in the same manner as in Example 1, except that copper chloride (CuCl) was used instead of calcium chloride (CaCl) and the aqueous solution concentration of each component was changed as shown in Table 1 below, and test pieces for adhesion tests were prepared.

[0094] (Comparative Example 1) According to Patent Document 1, a sheet-shaped adhesive composition was produced in the same manner as in Example 1, and a test piece for an adhesion test was prepared, except that a commercially available polyvinyl alcohol (PVA(2); degree of polymerization 1500, degree of saponification 86 to 90 mol%) not having a repeating unit represented by general formula (1) was used instead of the P-PVA(1) obtained in Synthesis Example 1, calcium chloride (CaCl2) was not used, and the aqueous solution concentration of each component was changed as shown in Table 1 below.

[0095] (Comparative Example 2) A sheet-shaped adhesive composition was produced in the same manner as in Example 1, except that a commercially available polyvinyl alcohol (PVA(1); degree of polymerization: 1300, degree of saponification: 99 mol % or more) not having a repeating unit represented by general formula (1) was used instead of the P-PVA(1) obtained in Synthesis Example 1, and the aqueous solution concentration of each component was changed as shown in Table 1 below. A test piece for an adhesion test was then prepared.

[0096] (Comparative Example 3) A sheet-shaped adhesive composition was produced in the same manner as in Example 1, and a test piece for an adhesion test was prepared, except that a commercially available polyvinyl alcohol (PVA(2); degree of polymerization 1500, degree of saponification 86 to 90 mol%) not having a repeating unit represented by general formula (1) was used instead of the P-PVA(1) obtained in Synthesis Example 1, and the aqueous solution concentration of each component was changed as shown in Table 1 below.

[0097] Comparative Example 4 A sheet-shaped adhesive composition was produced in the same manner as in Example 1, except that calcium chloride (CaCl2) was not used and the aqueous solution concentration of each component was changed as shown in Table 1, and a test piece for the adhesion test was prepared.

[0098] (Comparative Example 5) Test pieces for adhesion tests were prepared in the same manner as in Example 1, except that a commercially available fibrin adhesive (Bolheal (registered trademark) manufactured by KM Biologics Co., Ltd.) was applied to the surface of the pork.

[0099] (Test Example 1: Tensile Strength Test (Adhesion Test)) The upper end of the adhesion test specimen was fixed, and a plastic bottle was attached to the lower end with the mouth facing up. Water was poured into the mouth of the plastic bottle at a rate of approximately 50 g per minute, and the mass of water poured was measured when the adhesive surfaces of the pork slices had completely peeled off and fallen. Based on the obtained mass of poured water, the adhesive strength was calculated using the following formula (1). However, if the adhesion test specimen peeled off before the water was poured, the adhesive strength was recorded as 0 (zero). The results are shown in Table 1 and Figure 1.

[0100]

number

[0101] It is clear from Examples 1 to 7 that the adhesive composition of the present invention had a higher adhesive strength after a curing time of 10 minutes than Comparative Example 5, which used a commercially available fibrin-based adhesive. From the above, it is clear that the adhesive composition of the present invention has superior adhesive strength over a short period of time compared to conventional techniques.

[0102] In contrast, in Comparative Example 1, in which commercially available polyvinyl alcohol (PVA (2)) was used and calcium chloride (CaCl2) was not used, Comparative Example 2, in which commercially available polyvinyl alcohol (PVA (1)) was used, Comparative Example 3, in which commercially available polyvinyl alcohol (PVA (2)) was used, and Comparative Example 4, in which a phosphated polyvinyl alcohol compound was used and calcium chloride was not used, the test pieces for the adhesion test all peeled off before water was poured into the adhesion test, and no adhesion was observed at all.

[0103] [Table 1]

[0104] (Test Example 2: Flexibility Test) The adhesive composition was applied to the surface of a piece of pork in an area of ​​2.5 cm wide x 1.6 cm long, and then left to stand at room temperature (25°C) for 1 hour. The adhesive composition-coated surface was then observed while slowly stretching both ends of the coated area with both hands. If the coated surface was soft and the adhesive composition stretched by the same amount as the stretched length, the flexibility was rated as "present," and if the coated surface was hard, the flexibility was rated as "not present."

[0105] Example 8 The sheet-shaped adhesive composition described in Example 2 was used and evaluated in accordance with Test Example 2. The applied surface was soft after being left for 1 hour, and the sheet-shaped adhesive composition was confirmed to be stretchable by stretching the pork, confirming that the composition had flexibility.

[0106] (Comparative Example 6) A commercially available cyanoacrylate adhesive (Dermabond (registered trademark) manufactured by Johnson & Johnson) was used and evaluated in accordance with Test Example 2. The applied surface was hard, and no extensibility was observed even when the pork was stretched, confirming that it had "no" flexibility.

[0107] From the above, it was revealed that the adhesive composition of the present invention has both high adhesiveness and flexibility, whereas commercially available fibrin-based adhesives and cyanoacrylate-based adhesives were found to be inferior in either adhesiveness or flexibility.

Claims

1. (A) General formula (1): 【Chemistry 1】 [In the formula, R １ represents an oxygen atom or a bond. ２ indicates a hydrogen atom or a hydroxyl group. * indicates a repeating portion.] A repeating unit represented by the formula: General formula (2): 【Chemistry 2】 A polymer compound having a repeating unit represented by the formula: (B) a water-soluble polyphenol, and (C) a salt of at least one metal selected from the group consisting of alkaline earth metals, transition metals belonging to the fourth period of the periodic table, and aluminum An adhesive composition comprising:

2. The repeating units represented by general formula (1) contained in the polymer compound (A) are represented by general formulas (1A), (1B), and (1C): 【Transformation 3】 2. The adhesive composition according to claim 1, which contains at least one repeating unit selected from the group consisting of:

3. The repeating unit represented by general formula (1) contained in the polymer compound (A) is represented by general formula (1A): 【Chemistry 4】 The adhesive composition according to claim 2, which contains a repeating unit represented by the following formula:

4. 2. The adhesive composition according to claim 1, wherein the polymer compound (A) contains 3 to 60 mol % of the repeating unit represented by the general formula (1), where the total amount of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) is 100 mol %.

5. 2. The adhesive composition according to claim 1, wherein the water-soluble polyphenol compound (B) is at least one selected from the group consisting of hydroxybenzoic acid compounds, hydroxycinnamic acid compounds, flavonoid compounds, stilbene compounds, caffeic acid, chlorogenic acid, pyrogallol, gallic acid, catechin, hydrolyzable tannins, condensed tannins, and 3-theaflavin gallate.

6. 2. The adhesive composition according to claim 1, wherein the content of the water-soluble polyphenol compound (B) is 10 to 1,000 parts by mass per 100 parts by mass of the polymer compound (A).

7. 2. The adhesive composition according to claim 1, wherein the salt (C) is a salt of at least one metal selected from the group consisting of Fe, Zn, Mn, Cu, Ca, Mg, Al, Sr, and Ba.

8. 2. The adhesive composition according to claim 1, wherein said salt (C) is a chloride.

9. 2. The adhesive composition according to claim 1, wherein the salt (C) is a chloride of Ca.

10. 2. The adhesive composition according to claim 1, wherein the content of the salt (C) is 10 to 1000 parts by mass per 100 parts by mass of the polymer compound (A).

11. 10. The adhesive composition of claim 1 which is a solid adhesive.

12. The adhesive composition according to claim 1 , which is in the form of a sheet.

13. The adhesive composition according to any one of claims 1 to 12, which is a medical adhesive.

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