Claims
- 1. A method of adhering a dental material for use in any oral cavity comprising as a main component a compound represented by the formula ##STR10## wherein A is H, F, or CH.sub.3, and D is a fluoroalkyl group having 1 to 20 carbon atoms.
- 2. A method of adhesion according to claim 1 which comprises the compound of the formula (1) in the form of a monomer and/or a polymer thereof.
- 3. A method of adhesion according to claim 1 which mainly comprises the compound of the formula (1) and an other copolymerizable compound.
- 4. A method of adhesion according to claim 3 wherein the other copolymerizable compound is acrylic acid, methacrylic acid or an ester thereof.
- 5. A method of adhesion according to claim 4 wherein the acrylic or methacrylic ester is C.sub.1.about.20 alkyl ester thereof, or polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate or like ester of polyethylene glycol, trimethylolpropane or like polyalcohol.
- 6. A method of adhesion according to claim 3 wherein the other copolymerizable compound is .alpha.-fluoroacrylic acid or an ester thereof.
- 7. A method of adhesion according to claim 6, wherein the .alpha.-fluoroacrylic ester is selected from the group consisting of C.sub.1.about.20 alkyl esters thereof, polyethylene glycol di-.alpha.-fluoroacrylate, trimethylolpropane tri-.alpha.-fluorocrylate, the polyethylene glycol derivative thereof, trimethylolpropane and homologous polyalcohols.
- 8. A method of adhesion according to claim 7 wherein the other copolymerizable compound is methyl .alpha.-fluoroacrylate.
- 9. A method of adhesion according to claim 3 which comprises each of the compound of the formula (1) and the other copolymerizable compound in the form of a monomer and/or a polymer thereof.
- 10. A method of adhesion according to claim 1 which comprises the compound of the formula (1) in the form of (a) and (b),
- (a) a polymer obtained by polymerizing, as a part or whole of monomers, at least one compound selected from the group consisting of a compound of the formula ##STR11## an ester of a polyalcohol and a compound of the formula ##STR12## wherein A is H, F or CH.sub.3, E is C.sub.1.about.20 alkyl group or C.sub.1.about.20 fluoroalkyl group,
- (b) a monomer which is at least one compound selected from the group consisting of a compound of the formula ##STR13## an ester of a polyalcohol and a compound of the formula ##STR14## wherein A and E are same as above, provided that at least one of (a) component and (b) component contains C.sub.1.about.20 fluoroalkyl group.
- 11. A method of adhesion according to any of claims 1 to 10 which further contains an adhesive reactive monomer.
- 12. A method of adhesion according to claim 11 wherein the adhesive reactive monomer is 4-methacryloxyethyl trimellitic acid or an anhydride thereof.
- 13. A method of adhesion according to any of claims 1 to 10 which further contains a radical producing source.
- 14. A method according to claim 1 wherein the material is selected from the group consisting of dental material, bone artificial joint, and artificial bone constructed from made of ceramic, metal or the like.
- 15. A method as defined in claim 14 wherein the dental material is enamel or dentin.
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 62-245637 |
Sep 1987 |
JPX |
|
Parent Case Info
This application is a continuation of application Ser. No. 276,099 filed Sept. 27, 1988 now abandoned.
The present invention relates to an adhesive composition for biomaterial use which has an excellent adhesive strength.
Recently, for example, in therapy of teeth, a composite resin is developed in place of a dental coment. The recent composite resin is stable for a long period of time, small in water absorbency and destruction and some of them are not distinguished from a natural tooth in color tone.
However, the composite resin does not adhere to a dental material such as enamel or dentine, and accordingly separates from dental material during a long term of use.
Conventionally, various adhesives have investigated which improve adhesiveness between a composite resin and a dental material. However, many of adhesives have not developed which adhere firmly to the dental material for a long time, at a circumstance which is wet and great in temperature change, because many of adhesives have problems in durability in oral cavity and operability at use.
An object of the invention is to provide an adhesive composition having an excellent adhesiveness for a long time at a circumstance such as in oral cavity which is wet and great in temperature change and receives repeated strain by mastication.
Another object of the invention is to provide an adhesive composition for bonding a bone with a biomaterial such as an artificial joint, artificial bone made of ceramic, metal or the like.
The above and other objects of the invention will become apparent from the following description.
In an adhesive composition for biomaterial use, the present invention provides a composition characterized by comprising as a main component a compound represented by the formula ##STR2## wherein A is H, F or CH.sub.3, D is fluoroalkyl group having 1 to 20 carbon atoms.
IUPAC Macro '82, Amherst. July 12.about.16 (1982) discloses a dental repair composition comprising bisphenol A-bis-ethylene glycol dimethacrylate, octafluoropentyl methacrylate and silane-treated quartz powder, but the dental material obtained therefrom is silent about adhesiveness, although disclosed to have almost same strength and abrasion resistance as the conventional material. Further, Shika Zairyo. Kikai Vol. 2 No. 1 50-57 (1983) described a bulk polymerized polymer of 2,2,2-trifluoroethyl methacrylate (TFEMA) and methyl methacrylate (MMA), and a resin obtained by powder-liquid polymerization from poly-TFEMA (PTFEMA) as powder component and MMA as liquid component. This literature discloses about mechanical properties, etc. but is mute about adhesiveness. JP-A-62-33110 discloses a dental material comprising a polymer containing at least 40% by weight of a structure unit of the formula ##STR3## wherein R is aliphatic group having 1 to 5 carbon atoms. This polymer is disclosed to be suitable as a dental material such as denture base but nothing about adhesiveness of the polymer is described.
In the present invention, the substituent D of the formula (1) is fluoroalkyl group having 1 to 20, preferably 1 to 10 carbon atoms. Examples of the compound of the formula (1) are trifluoroethyl methacrylate (3FMA), tetrafluoropropyl methacrylate (4FMA), pentafluoropropyl methacrylate (5FMA), octafluoropentyl methacrylate (8FMA), heptadecafluorononyl methacrylate (17FMA), trifluoroethyl .alpha.-fluoroacrylate (3FFA), tetrafluoropropyl .alpha.-fluoroacrylate (4FFA), pentafluoropropyl .alpha.-fluoroacrylate (5FFA), octafluoropentyl .alpha.-fluoroacrylate (8FFA) and heptadecafluorononyl .alpha.-fluoroacrylate (17FFA). These are used singly or as a mixture of at least two of them. The compound of the formula (1) is used in the form of a monomer and/or a polymer thereof, or conjointly with an other copolymerizable compound.
Preferable examples of the other copolymerizable compounds are acrylic acid, methacrylic acid, .alpha.-fluoroacrylic acid and esters of these acids. As esters of (meth)acrylic acid and .alpha.-fluoroacrylic acid are preferable esters having alkyl of 1 to 20 carbon atoms and esters with a polyalcohol.
Examples of alkyl esters of (meth)acrylic acid are methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate and hexadecyl (meth)acrylate. Examples of alkyl esters of .alpha.-fluoroacrylic acid are methyl .alpha.-fluoroacrylate, ethyl .alpha.-fluoroacrylate, butyl .alpha.-fluoroacrylate, octyl .alpha.-fluoroacrylate, dodecyl .alpha.-fluoroacrylate and hexadecyl .alpha.-fluoroacrylate.
Examples of polyalcohols are trimethylolpropane, polymethylene (or ethylene) glycol of the formula HO--(CH.sub.2)n--OH, n:1 to 5, and compounds of the formulae ##STR4##
As an other copolymerizable compound can be used urethane methacrylate represented by the formula ##STR5##
These copolymerizable compounds can be used together with the compound of the formula (1) in the form of a monomer and/or a polymer thereof.
As a more preferable embodiment, the present invention provides an adhesive composition which comprises the compound of the formula (1) in the form of (a) and (b),
(a) a polymer obtained by polymerizing, as a part or whole of monomers, at least one compound selected from the group consisting of a compound of the formula ##STR6## an ester of a polyalcohol and a compound of the formula ##STR7## wherein A is H, F or CH.sub.3, E is C.sub.1.about.20 alkyl group or C.sub.1.about.20 fluoroalkyl group,
(b) a monomer which is at least one compound selected from the group consisting of a compound of the formula ##STR8## an ester of a polyalcohol and a compound of the formula ##STR9## wherein A and E are same as above, provided that at least one of (a) component and (b) component contains C.sub.1.about.20 fluoroalkyl group.
The polymer of (a) component can be prepared by homopolymerizing a monomer of the formula CH.sub.2 .dbd.C(A)COOD, A and D are same as above, or by copolymerizing at least 10% and less than 100% by weight of the above monomer and up to 90% by weight of an other copolymerizable monomer. The copolymerizable monomer includes the above copolymerizable compound for the compound of the formula (1), such as (meth)acrylic acid, .alpha.-fluoroacrylic acid, alkyl ester or polyalcohol ester of these acids, and the above-mentioned urethane methacrylate.
As a monomer of the formula (2) are used the compounds enumerated in the above compound of the formula (1), and methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, methyl .alpha.-fluoroacrylate, ethyl .alpha.-fluoroacrylate, butyl .alpha.-fluoroacrylate, octyl .alpha.-fluoroacrylate, dodecyl .alpha.-fluoroacrylate and hexadecyl .alpha.-fluoroacrylate. These compounds can be used singly or as a mixture of at least two of them.
In the present invention, an adhesive reactive monomer can be used as required. The monomer includes a compound having hydroxyl group (--OH), carboxyl group (--COOH), phosphoric acid group (--PO.sub.4 H.sub.2), mercapto group (--SH), sulfonic acid group (--SO.sub.3 H), cyano group (--CN), isocyanato group (--NCO), etc. Examples thereof are N-(2-hydroxy-3-methacryloxypropyl)-N-phenylglycine (NPG-GMA), methacryloxyethyl phthalate, N-methacrylyl-N'-carboxymethyl piperazine (N1), N-methacrylyl-N,N'-dicarboxymethyl p-phenylenediamine (N2), 4-methacryloxyethyl trimellitic acid (4-MET), 4-methacryloxyethyl trimellitic acid anhydride (4-META), methacryloxyethyl phosphate, N-(4-mercaptophenyl)methacrylamide and N-O-dimethacryloyl tyrosine. These compounds can be used singly or as a mixture of at least two of them. The adhesive reactive monomer is used preferably in an amount of 1 to 20% by weight based on the total amount of the monomers.
The polymer of the compound of the formula (1) of the present invention, or copolymer thereof with an other copolymerizable compound can be prepared by polymerizing the above monomers by a method used in the polymerization of an ethylenically unsaturated monomer, preferably in the presence of a radical producing source. In order to produce a radical, a polymerization initiator is added to a monomer or ultraviolet ray or visible ray is irradiated to a monomer.
A polymerization initiator is usually used which decomposes at around room temperature to produce a radical. Examples of polymerization initiators are tri-n-butyl-borane (TBB) and like metal alkylates which react with oxygen to form a radical, peroxides (benzoyl peroxide, acetyl peroxide, lauroyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl peroxybenzoate, etc.) and a combination of the peroxide and an accelerator (tertiary amine, cobalt naphthenate or octenoate, transition metal ion, amine salt of p-toluenesulfonic acid or sulfinic acid, etc.). The above respective polymerization initiator and accelerator is used preferably in an amount of about 0.1 to 2.5 parts by weight per 100 parts by weight of total amount of the monomers.
In case of the polymerization with the irradiation of ultraviolet ray or visible ray, a photosensitizer is usually used. In the irradiation of ultraviolet ray, benzophenone, nitrofluorene, 5-nitroacenaphthene or the like can be used, and in the irradiation of visible ray, camphorquinone or the like can be used.
The polymer of the present invention having a structural unit of the formula (1) is excellent, for example, particularly in dimensional stability and non-water-absorbency. The above-mentioned JP-A-62-33110 discloses a homopolymer having a structural unit of the formula (3), and a copolymer of the monomer of the formula (3) and a monomer represented by the formula
US Referenced Citations (7)
Foreign Referenced Citations (1)
| Number |
Date |
Country |
| 0075191 |
Mar 1983 |
EPX |
Continuations (1)
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Number |
Date |
Country |
| Parent |
276099 |
Sep 1988 |
|
Patent Grant
5061184
