JPH0751695B2 - Adhesive composition for biomaterial - Google Patents

Description

TECHNICAL FIELD The present invention relates to an adhesive composition for biomaterials having excellent adhesive strength.

(Prior art) In recent years, composite resins have been developed as an alternative to dental cement in the treatment of teeth, for example, and recently, they are stable over a long period of time, have little water absorption and disintegration, and cannot be distinguished from natural teeth. It has become possible to make products with such a color tone.

However, since the composite resin does not essentially adhere to tooth enamel, dentin, and other tooth substances, the composite resin may eventually fall off within a long period of time.

Conventionally, various adhesives have been developed to improve the adhesion between biomaterials such as composite resin and tooth material, but there are problems with durability in the oral cavity and operability during use. Many of them exist, and few of them wet like the oral cavity and strongly adhere to the tooth structure for a long period of time in an environment where the temperature changes drastically.

(Problems to be Solved by the Invention) An object of the present invention is to provide excellent adhesiveness to dentin mainly composed of calcium phosphate, living bones, etc., and particularly long-term stable adhesive force under humid conditions such as in vivo. To provide an adhesive composition for a biomaterial.

More specifically, the object of the present invention is for a biomaterial that exhibits excellent adhesiveness over a long period of time in an environment where the temperature changes drastically under moist conditions such as the oral cavity and the cyclic strain force associated with chewing is applied. An object is to provide an adhesive composition.

Another object of the present invention is to provide an adhesive composition for biomaterials, which is useful for adhering biomaterials to biomaterials such as artificial joints and artificial joints made of ceramics, metals and the like.

(Means for Solving Problems) The present invention relates to an adhesive composition for a biomaterial, which has the general formula (In the formula, A represents F and B represents a fluoroalkyl group having 1 to 20 carbon atoms) as a main constituent component, and relates to an adhesive composition for biomaterials.

IUPAC Macro'82, Amherst. July 12-16 (1982) discloses a dental restorative composition comprising bisphenol A-bis-ethylene glycol dimethacrylate, octafluoropentyl methacrylate and silanized quartz powder. However, although it is stated that the dental material obtained from this is almost the same in strength and abrasion resistance as conventional ones, there is no disclosure about adhesiveness. In addition, Dental Materials and Instruments Vol.2 No.1 50-57 (1983) uses bulk polymer of 2,2,2-trifluoroethylmethacrylate (TFEMA) and methylmethacrylate (MMA) or powder liquid polymerization method. It describes the mechanical properties of a resin that combines poly-TFEMA (PTFEMA) as the powder component and MMA as the liquid component, but does not mention anything about the adhesiveness. Further, in JP-A-62-33110, a general formula A dental material comprising a polymer containing 40% by weight or more of a structural unit represented by the formula (wherein R represents an aliphatic group having 1 to 5 carbon atoms) is disclosed. However, although it is described that this polymer is suitable for dental materials such as denture base, there is no disclosure regarding adhesiveness.

In the present invention, the substituent B in the general formula (1) has 1 carbon atom.
~ 20, preferably 1-10 fluoroalkyl groups.
Specific examples of the compound of the general formula (1) include, for example, trifluoroethyl α-fluoroacrylate (3FFA), tetrafluoropropyl α-fluoroacrylate (4FFA),
Pentafluoropropyl α-fluoroacrylate (5F
FA), octafluoropentyl α-fluoroacrylate (8FFA), heptadecafluorononyl α-fluoroacrylate (17FFA) and the like. At least one of these may be used.

In a further preferred embodiment of the present invention, a trifluoroethyl methacrylate polymer and methyl α-
An adhesive composition for biomaterials having excellent adhesion to dentin, which is composed of a monomer of fluoroacrylate and trifluoroethyl α-fluoroacrylate, can be mentioned.

In the present invention, an adhesive reactive monomer can be used if necessary. Adhesive reactive monomers include hydroxyl groups (-OH), carboxylic acid groups (-COOH), phosphoric acid groups (-PO)
₄ H ₂ ), mercapto group (-SH), sulfonic acid group (-SO
₃ H), cyano group (-CN), isocyanate group (-NCO)
A monomer having, for example, N- (2
-Hydroxy-3-methacryloxypropyl) -N-
Phenylglycine (NPG-GMA), methacryloxyethyl phthalate, N-methacrylyl-N'-carboxymethylpiperazine (N1), N-methacrylyl-N, N'-dicarboxymethyl p-phenylenediamine (N2), 4 -Methacryloxyethyl trimellitic acid (4-MET), 4-
Methacryloxyethyl trimellitic anhydride (4-MET
A), methacryloxyethyl phosphate, N- (4
Examples thereof include -mercaptophenyl) methacrylamide and N-O-dimethacryloyltyrosine. At least one of these may be used. The use ratio of the adhesive reactive monomer is preferably about 1 to 20% by weight based on the total amount of the monomers.

The polymer of the compound of the general formula (1) of the present invention is obtained by polymerizing the above-mentioned monomer, preferably in the presence of a radical generating source, by a polymerization method usually used for polymerizing an ethylenically unsaturated monomer. It can be prepared, and the radical can be generated by, for example, adding a polymerization initiator to the monomer or irradiating the monomer with ultraviolet rays or visible light.

As the polymerization initiator, one that decomposes at room temperature to generate a radical is usually used. The polymerization initiator is, for example, tri-n.
-Alkyl metals that react with oxygen such as butylborane (TBB) to generate radicals, peroxides (benzoyl peroxide, acetyl peroxide, lauroyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl peroxy) Benzoate, etc.), the above-mentioned peroxide and promoter (tertiary amine, cobalt salt of naphthenic acid or octenoic acid, transition metal ion, p-
Examples thereof include a combination of toluenesulfonic acid and amine salt of sulfinic acid. It is preferable that the above-mentioned polymerization initiator and accelerator are usually used in a ratio of about 0.1 to 2.5 parts by weight based on 100 parts by weight of all monomers used.

When the monomer is irradiated with ultraviolet rays or visible rays to carry out polymerization, a photosensitizer is usually used. When the photosensitizer is irradiated with ultraviolet rays, benzophenone, nitrofluorene, 5-
When irradiating with visible light such as nitroacenaphthene, it is camphorquinone.

The polymer having the structural unit of the general formula (1) of the present invention is particularly excellent in, for example, dimensional stability and non-water absorption. In the above-mentioned JP-A-62-33110, a homopolymer consisting of a structural unit of the general formula (2), a monomer of this structural unit and a general formula CH ₂ ═C (F) COOR ¹ or CH ₂ ═C Disclosed is a copolymer with a monomer represented by (R ² ) COOR ¹ (wherein R ¹ represents a fluorine-containing aliphatic group having 1 to 5 carbon atoms, and R ² represents hydrogen or a methyl group). However, the above-mentioned polymer of the present invention is far superior in dimensional stability and non-water absorbability to the polymer described in JP-A-62-33110 shown in Comparative Example 1 below. , More useful.

(Examples) Examples, comparative examples and reference examples will be described below.
The term "parts" means "parts by weight".

Examples 1 to 5 0.5 parts of benzoyl peroxide was added to 100 parts of fluorine-containing acrylic acid ester shown in Table 1 and mixed well,
The mixture was put into glass tubes having inner diameters of 4 mm, 6 mm and 10 mm, respectively, and kept at 55 ° C. for 24 hours and further at 100 ° C. for 15 hours to polymerize each fluorine-containing acrylate ester.

The properties of the obtained polymer were measured by the following methods, and it was confirmed that the polymer was suitable for biomaterials. The results are shown in Table 1.

(1) Critical surface tension γc [dyn / cm] A sheet having a thickness of 3 mm was formed, and the wetting angle was measured with various solvents to determine the critical surface tension.

(2) Hardness The hardness was measured with a Rockwell hardness meter M scale (load is 60 kg). Test piece: 3mm thick sheet.

(3) Breaking strength TS [kg / cm ² ] The tensile strength was measured with a tensile tester at a crosshead of 3.0 mm / min. Test piece: 45 mm x 5 mm x 0.5 mm (length x width x thickness).

(4) Water absorption rate [%] The same test piece as in (3) was dried at 50 ° C for 24 hours, then allowed to stand in water at 23 ° C, and the weight change after 24 hours was measured.

(5) Dimensional stability [%] At the time of measuring (4), a change in length was measured at the same time to obtain dimensional stability.

Comparative Example 1 Methyl α-fluoroacrylate (MFA) as a monomer
A polymer was obtained in the same manner as in Example 1 except that was used, and the characteristics were measured in the same manner. The results are also shown in Table 1.

In the table, A and B represent the substituents A and B of the general formula (1).

Example 6 and Comparative Examples 2 to 4 P3FMA powder 0.1 g, 4-META (0.005 g), 0.095 g of the mixed monomer shown in Table 2 and TBB (0.007 g) were mixed with an adhesive agent to prepare bovine teeth. After adhesion with a metal (SUS 304) and immersion in water at 37 ° C for the period shown in the table, the tensile adhesion strength (kgf / cm ² ) was measured 5 times, and the average value is shown in Table 2. Since each adhesive adheres well to the tooth substance and peels off between the adhesive and the metal, the tensile adhesive strength between the adhesive agent and the tooth substance is larger than the values shown in Table 2.

(Advantages of the Invention) The adhesive composition for biomaterials of the present invention is excellent over a long period of time in an environment where the temperature changes drastically under humid conditions such as the oral cavity, and moreover, the repeated strain force associated with mastication is applied. Shows adhesiveness. Until now, adhesives using MMA have not been very effective as dentin adhesives, and particularly lack long-term durability in water. When the MMA is changed to the compound of the general formula (1), especially the compound of the general formula (1) and MFA, not only the initial adhesiveness is increased, but also the adhesive strength is hardly changed over a long period of time. Shows sex.

Further, the adhesive of the present invention is useful for bonding living bones to artificial materials such as artificial joints and artificial bones composed of ceramics and metal, and like the above, it has excellent adhesiveness and is stable for a long period of time. Shows the adhesive strength.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 62-33110 (JP, A) JP 61-21110 (JP, A) JP 61-209 (JP, A)

Claims (2)

[Claims] 1. In the adhesive composition for biomaterial, the general formula An adhesive composition for a biomaterial, comprising a compound represented by the formula (wherein A represents F and B represents a fluoroalkyl group having 1 to 20 carbon atoms) as a main constituent. 2. The method according to claim 1, which is excellent in the adhesiveness between the trifluoroethyl methacrylate polymer and the dentin composed of the monomers of methyl α-fluoroacrylate and trifluoroethyl α-fluoroacrylate. Adhesive composition for biomaterial.