JPH01152179A - Adhesive composition for biotic material - Google Patents

Abstract

PURPOSE:To provide an adhesive compsn. for biotic materials which is excellent in adhesion to dentin, living bones, etc., mainly composed of calcium phosphate and particularly exhibits a stable long-term adhesion under such wet conditions as lining organisms, by using a specific fluorinated acrylic ester as the main constituent. CONSTITUTION:An adhesive compsn. for biotic materials is made up of a compd. of formula I (wherein A is H, F or CH3; and B is 1-20C fluoroalkyl), or contains as the main constituents the above-mentioned compd. and other compd. copolymerizable therewith. The compd. of formula I, or the above-mentioned compd. and other compd. copolymerizable therewith may be used in the form of a monomer(s) and/or a polymer thereof. Examples of the above-mentioned other copolymerizable compd. include acrylic acid, methacrylic acid, and esters thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an adhesive composition for biological materials having excellent adhesive strength.

(Prior art) In recent years, composite resins have been developed as an alternative to dental cement in dental treatment, for example, and have recently become stable over a long period of time, have low water absorption and disintegration (and are indistinguishable from natural teeth). Colors that were previously not available began to be made.

However, since composite resin essentially does not adhere to tooth substances such as tooth enamel and dentin, the Combo Knot Lennon may eventually fall off over a long period of time.

In the past, various adhesives have been developed to improve the adhesion between biomaterials such as composite resins and tooth structure, but there are problems with their durability in the oral cavity and ease of use. There are many such materials, but there are few that can strongly adhere to the tooth structure over a long period of time in an environment as moist as the inside of the oral cavity and with rapid temperature changes.

(Problems to be Solved by the Invention) The purpose of the present invention is to provide excellent adhesion to tooth tissue, living bone, etc., which is made mainly of calcium phosphate, and to provide stable adhesion for a long period of time, especially under humid conditions such as in vivo. An object of the present invention is to provide an adhesive composition for biomaterials that exhibits strength.

More specifically, the object of the present invention is to develop a biological material that exhibits excellent adhesive properties over a long period of time under humid conditions such as in the oral cavity, where temperature changes are large, and where repeated straining forces are applied due to mastication. An object of the present invention is to provide an adhesive composition for materials.

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

(Means for Solving the Problems) The present invention provides an adhesive composition for biomaterials, which has a general formula (wherein A is H%F or OH, and B has 1 to 20 carbon atoms.
The present invention relates to an adhesive composition for biomaterials, which contains as a main component a compound represented by (a fluoroalkyl group), or the compound and another compound copolymerizable with the compound.

Furthermore, I UPAC Macro '82* A*
Herst, July 12-16 (1982) discloses a dental restorative composition comprising bisphenol A-bis-ethylene glycol dimethacrylate, octafluoropentyl methacrylate, and silanized quartz powder; Although it is stated that the strength and abrasion resistance of the materials used are almost the same as conventional ones,
There is no disclosure regarding adhesive properties. In addition, 2t212- ) 17 Fluoroethyl methacrylate (TFEMA) and Methyl methacrylate (MMA)
Poly T is used as a bulk polymer, or as a powder component in the powder-liquid polymerization method.
Although it describes the mechanical properties of a resin that combines FEMA (PTFEMA) and MMA as a liquid component, there is no mention of adhesive properties. A dental material made of a deciduous body containing 40% by weight or more of a structural unit represented by C82C(3) oo R (wherein R represents an aliphatic group having 1 to 5 carbon atoms) is disclosed. However, although it is stated that this polymer is suitable for dental materials such as denture bases, nothing is disclosed about adhesive properties.

In the present invention, substituent B in the above general formula (1) has 1 carbon number.
Specific examples of compounds of general formula (1) having 1 to 20, preferably 1 to 10 fluoroalkyl groups include trifluoroethyl methacrylate (3FMA), tetrafluoropropyl methacrylate (4FMA), and pentafluoropropyl methacrylate (4FMA). Fluoropropyl methacrylate (5FMA), octafluoropentyl methacrylate (8FMA), heptadecafluorononyl methacrylate (17FMA)
,) Lifluoroethyl meifluoroacrylate (3F
FA), tetrafluoropropyl a-fluoroacrylate (4F F A ), pentafluoropropyl α-
fluoroacrylate) (5FFA), octafluoropentyl a-fluoroacrylate (8FFA), heptadecafluorononyl meifluoroacrylate (17F
F A ), etc. can be exemplified. At least one kind of these can be used. These general formulas (1
) can be used in the form of a monomer and/or in the form of a polymer obtained by polymerizing it, and can also be used together with other compounds copolymerizable with it.

Preferred examples of other copolymerizable compounds include acrylic acid, methacrylic acid, α-7 tetraoacrylic acid, and esters thereof, and examples of these esters include, for example, those having an alkyl group having 1 to 20 carbon atoms. Ester or ester with polyhydric alcohol is preferred.

Examples of the fullyl ester of acrylic acid or methacrylic acid include methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, hexadecyl acrylate, methyl methacrylate, dithyl methacrylate, butyl methacrylate, octyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate, etc. Examples of alkyl esters of a-fluoroacrylic acid include methyl a-fluoroacrylate, ethyl a-fluoroacrylate, butyl a-fluoroacrylate, and octyl a-fluoroacrylate.
-fluoroacrylate, dodecyl α-fluoroacrylate, hexadecyl a-'fluoroacrylate, and the like.

Examples of the polyhydric alcohol include borinotylene (or ethylene) glycol represented by HO(CH2)nOH (wherein n is 1 to 5), trinotyrolpropane, or compounds represented by the formula. Further, as other copolymerizable compounds, urethane methacrylate represented by the formula % can also be used.

These other copolymerizable compounds can also be used together with the compound of general formula (1) in the form of monomers and/or in the form of polymers obtained by polymerizing them.

In a further preferred embodiment of the present invention, the compound of general formula (1) is at least one compound selected from the group of esters of CH2=C-COOH and polyhydric flucol.
The form of a polymer (in the formula, A represents HlF or CHs, and D represents a fluoroalkyl group having 1 to 20 carbon atoms) and (b) general formula % in which the species is part or all of the monomer. Formula % CH2 = C-Adhesive composition containing at least one monomer selected from the group of esters of COOH and polyhydric alcohol (in the formula, A and D are the same as above) [where a At least one of component () and component (b) contains a fluoroalkyl group having 1 to 20 carbon atoms.

The polymer of component (a) above is obtained by homopolymerizing monomers represented by the general formula % (1) (wherein A and B are the same as above), or by homopolymerizing monomers represented by the general formula % (1) (wherein A and B are the same as above), or by polymerizing the above monomers in an amount of 10% by weight or more. ,1
It is produced by copolymerizing less than 00% by weight of other copolymerizable monomers with 90% by weight or less of other copolymerizable monomers. Other copolymerizable monomers include compounds copolymerizable with the compound of general formula (1) described above, i.e., acrylic acid, methacrylic acid, a-fluoroacrylic acid, or alkyl esters thereof as described above; Examples include esters with polyhydric alcohols and the aforementioned urethane methacrylates.

As the monomer of general formula (2), in addition to the monomers exemplified as the compound of general formula (1), for example, methyl 7
Acrylate, ethyl acrylate, butyl acrylate, octyl 7-acrylate, dodecyl acrylate, hexadecyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate, methyl a-fluoroacrylate,
Examples include ethyl a-fluoro heptacrylate, butyl a-fluoroacrylate, octyl a-fluoroacrylate, dodecyl mefluoroacrylate, and hexadecyl a-fluoroacrylate. At least one kind of these can be used.

In the present invention, an adhesive reactive monomer can be used if necessary. Adhesive reactive monomers include hydroxyl group (-OH), carboxylic acid group (-COOH), phosphoric acid group (-PO, H2), mercapto group (-8H), and sulfonic acid group (-3O, H). , a cyano group (-CN), an incyanate group (-N GO), etc., and a specific example is N-(2-hydroxy-3-methacryloxypropyl)-N-phenylglycine (NPC-
GMA), methacryloxyethyl 7-talate, N-methacrylyl-N'-carboxymethylpiperazine (Nl)
.
), methacryloxyethyl phosphate, N-(4-
Examples include (mercaptophenyl) methacrylamide, N-0-methacryloyltyrosine, and the like. At least one kind of these can be used. The proportion of the adhesive reactive monomer used is preferably about 1 to 20% by weight based on the total amount of monomers.

The polymer of the compound of general formula (1) of the present invention, or the copolymer of the compound with another compound copolymerizable with it, can be produced by the above-mentioned polymerization method that is normally used when polymerizing ethylenically unsaturated monomers. by polymerizing the polymer, preferably in the presence of a radical generating source. R9J can be generated, and radicals can be generated, for example, by adding a polymerization initiator to the monomer or by irradiating the monomer with ultraviolet rays or visible light.

The polymerization initiator that is usually used is one that decomposes around room temperature and generates radicals.
- Alkyl metals and peroxides that react with oxygen to generate radicals such as butylporane (TBB) (benzoyl peroxide, acetyl peroxide, lauroyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl peroxide) benzoates, etc.), peroxides and promoters (tertiary amines, cobalt salts of naphthenic or octenoic acids, transition metal ions, p-
Examples include combinations of toluenesulfonic acid, amine salts of sulfinic acid, etc.). The polymerization initiator and accelerator are preferably used in an amount of usually 0.1 to 2.5 parts by weight based on 100 parts by weight of the total monomers used.

When polymerizing monomers by irradiating them with ultraviolet or visible light, a photosensitizer is usually used. Photosensitizers include benzophenone, nitrofluorene, 5-nitroacenaphthene, etc. when irradiated with ultraviolet rays, and can 7 when irradiated with visible light.
Akinon et al.

The polymer having the structural unit of general formula (1) of the present invention has particularly excellent dimensional stability and non-water absorbing property, for example.

The above-mentioned JP-A-62-33110 discloses a homopolymer consisting of the structural unit of the general formula (3), and the monomer of this structural unit and the general formula (%): (wherein, R1 is a carbon number of 1 -5 fluorine-containing aliphatic group, R2
represents a hydrogen or methyl group), and the above-mentioned polymer of the present invention is disclosed in the above-mentioned JP-A-62-33110, which is shown in Comparative Example 2 below. Compared to the described polymers, it has much better dimensional stability and non-water absorbing properties and is useful as a layer.

(Example) Examples, comparative examples, and reference examples will be described below. Note that parts simply indicate parts by weight.

Examples 1 to 10 0.5 part of benzoyl peroxide was added to 100 parts of the fluorine-containing acrylic ester listed in Table 1, and after mixing well, the mixture was placed in a plus tube with an inner diameter of 4-161 mm and 10 mm, respectively. , 24 hours at 55℃, then 1 hour at 100℃
The mixture was kept for 5 hours to polymerize each fluorine-containing acrylic ester.

The properties of the obtained polymer were measured using the method described below, and it was confirmed that it was suitable as a biomaterial. The results are shown in Table 1.

(1) Critical surface tension γc (dyn/am) The wetting angle was measured using various solvents using a 3-mm thick sheet.
The critical surface tension was determined.

(2) Hardness Measured using Rockwell hardness tester M scale (load is 60kg)
) Test piece: sheet-like with a thickness of 31 mm.

(3) Breaking strength T S (kg/c theory 2) Crosshead 3.0 transport/II by tensile tester! The measurement was carried out under the conditions of n. Test piece: 45msX5m@X005mm (
length x width x thickness).

(4) Water absorption rate [%] After drying the same test piece as in (3) at 50°C for 24 hours,
The sample was left in water at a temperature of 0.degree. C., and the weight change after 24 hours was measured.

(5) Dimensional stability [%] When measuring (4), the change in length was also measured at the same time to determine the dimensional stability.

Comparative Examples 1-2 Polymers were obtained in the same manner as in Example 1, except that methylnotacrylate (MMA) or methyl a-fluoroacrylate (MFA) was used as the monomer, and the properties were measured in the same manner. . The results are also shown in Table 1.

In addition, in the table, A and B are substituents A and B of general formula (1).
shows.

Example 11 Polymethyl methacrylate (PMMA) powder 0, Ig
, 4-methacryloxyethylsilimeriz) acid anhydride (
4-META) 5-g, MMA (0,076g), 3
FMA (0,019g) and) 9-n-butylborane (TBB) 0,007. Adhesion is carried out using stainless steel rods using an adhesive prepared by mixing the
After being immersed in water at 37° C. for 45 days, the tensile adhesive strength was measured and found to be 56 kgf/am”.

Example 12 In Example 11, M M A (0,057 g), 3
The tear strength was measured in the same manner except that FMA (0,038 g) was used, and it was found to be 76 kgf/as''.

Example 13 Polytriple oethylnotacrylate (P3FMA)
powder of 0. Ig, 4-META (5-g), MMA (
Using an adhesive prepared by mixing 0,095 g) and TB B (0,007 g), adhesive was bonded by mating stainless steel rods, and after immersion in water at 37°C for 45 days, the tensile adhesive strength was measured. However, 141kg4/
It was Cs2.

Example 14 In Example 13, instead of M M A (0,095 g), M M A (0,055 g) and 3 F M A
The tensile adhesive strength was measured in the same manner except that (0,0408 g) was used, and it was found to be 64 kg4/cv*2.

Comparative Example 3 The tensile adhesive strength was measured in the same manner as in Example 11 except that MMA (0,095 g) was used and 3FMA was not used, and it was found to be 45 kgf / 0 m2.

Comparative Example 4 PMMA powder 0. Using an adhesive prepared by mixing IgSM MA (0, Ig) and TBB (0,007 g), the raw tooth dentin and metal (SUS 304) were bonded,
After being immersed in water at 37°C for 50 hours, the tensile adhesive strength was measured and found to be 12 kg4/cm'.

Reference Example 1 3 obtained by copolymerization at the proportions (wt%) listed in Table 2
FFA and MMA copolymer test piece (10φX1mm)
American Dental As5oci
After storage in water at 37° C. for 7 days, water absorption (-g/cm 2 ) was measured based on the ADA (ADA) standard. The results are shown in Table 2.

2nd R Examples 15-18 P3FMA3F0. Ig, 4-META (
0,005g), 0,095g of the monomer shown in Table 3. A natural tooth and metal (SUS 304) were bonded using an adhesive prepared by mixing and T B B (0,007 g), and after being immersed in water at 37°C for the period specified in the table, the tensile bond strength was determined. (kgf/cm") was measured five times, and the average value is shown in Table 3. It should be noted that each adhesive adheres well to the tooth structure,
Because of the peeling between the adhesive and the metal, the tensile bond strength between the adhesive and the tooth structure is greater than the values shown in Table 3.

Comparative Example 5 0.1 g of PMMA powder, 4 META (0,005
g), MM A (0,095,) and T B B (
The procedure was the same as in Example 15 except that 0,007 g) was used, and the results are shown in Table 3.

Table 3 Examples 19-22 P3FMA3F0. Ig, 4-META
(0,0058), mixed monomer shown in Table 4 0.09
Example 1 except that 5g and TBB (0,007g) were used.
5, and the results are shown in Table 4. It should be noted that each adhesive adheres well to the tooth structure and peels between the adhesive and the metal, so
The tensile bond strength between the adhesive and the tooth substance is greater than the values given in Table 4.

Table 4 (Effects of the Invention) The adhesive composition for biomaterials of the present invention can be used for a long period of time under humid conditions, such as in the oral cavity, where temperature changes are severe and where repeated strain forces are applied due to mastication. Excellent 6
Indicates one-wearability. Adhesives using MMA to date have not been very effective as adhesives for dentin, and in particular lack long-term underwater durability. Compound and MFA not only increase the initial adhesion but also show surprising wet durability with little change in adhesion over a long period of time.

Compared to the conventional adhesive of Comparative Example 5, the adhesive of the present invention exhibits excellent long-term adhesion even to enamel.
In this way, showing similar excellent properties in both enamel and dentin is extremely advantageous in dental clinical practice.

In addition, the adhesive of the present invention is useful for adhering living bones to biomaterials such as prosthetic joints and artificial bones made of ceramics, metals, etc. As mentioned above, the adhesive has excellent adhesive properties and is stable over a long period of time. Indicates adhesive strength.

(that's all) Sender: Daikin Industries, Ltd. Representative Patent Attorney 1) Iwao Mura

Claims (4)

[Claims] (1) In adhesive compositions for biological materials, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, A is H, F or CH_3, and B has 1 to 2 carbon atoms.
0 fluoroalkyl group),
Or an adhesive composition for biomaterials, which contains the compound and another compound copolymerizable with the compound as main components. (2) Claims containing the compound of general formula (1), or the compound and other compounds copolymerizable with it, in the form of monomers and/or in the form of polymers obtained by polymerizing them. The adhesive composition according to item 1. (3) The adhesive composition according to claim 1 or 2, wherein the other copolymerizable compound is acrylic acid, methacrylic acid, or an ester thereof. (4) Compound of general formula (1) (a) Group of esters of general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and polyhydric alcohols A polymer in which part or all of the monomer is at least one compound selected from and (b) at least one monomer selected from the group of general formulas ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and the group of esters with polyhydric alcohols (wherein A and D are the same as above) [provided that at least one of component (a) and component (b) has 1 carbon atom ~20 fluoroalkyl groups].