CA2026417C - Dental adhesives - Google Patents
Dental adhesivesInfo
- Publication number
- CA2026417C CA2026417C CA002026417A CA2026417A CA2026417C CA 2026417 C CA2026417 C CA 2026417C CA 002026417 A CA002026417 A CA 002026417A CA 2026417 A CA2026417 A CA 2026417A CA 2026417 C CA2026417 C CA 2026417C
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- meth
- acrylate
- glyceryl mono
- polymerizable monomer
- dental adhesive
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Abstract
According to the present invention, a dental adhesive comprising glyceryl mono(meth)acrylate and a polymerizable monomer having at least one olefinic double bond and capable of coplymerizing with said glyceryl mono(meth)-acrylate is provided.
Description
202641~
TITLE
DENTAL ADHESIVES
FIELD OF THE INVENTION
This invention relates to dental adhesives having excellent properties of bonding a tooth and a dental restorative material together, and having excellent properties of marginal sealing between the tooth and material thus bonded.
BACKGROUND OF THE INVENTION
In the field of dental goods and materials, there have recently been developed various adhesives having excellent adhesiveness to a tooth, especially to a dentinal portion thereof. Used as adhesive components in such adhesives as referred to above are polymerizable monomers having acid groups in the molecule. These polymerizable monomers which are known, per se, include (meth)acrylate monomers such as those having in the molecule phosphoric acid diester groups ~Japanese Patent L-O-P Publn. No. 113089/1977), phosphoric acid monoester groups (Japanese Patent L-O-P Publn. No.
21607/1983), carboxyl group or acid anhydride groups (Japanese Patent L-O-P Publn. No. 11149/1979) and acid halide groups (Japanese Patent L-O-P Publn. No.
TITLE
DENTAL ADHESIVES
FIELD OF THE INVENTION
This invention relates to dental adhesives having excellent properties of bonding a tooth and a dental restorative material together, and having excellent properties of marginal sealing between the tooth and material thus bonded.
BACKGROUND OF THE INVENTION
In the field of dental goods and materials, there have recently been developed various adhesives having excellent adhesiveness to a tooth, especially to a dentinal portion thereof. Used as adhesive components in such adhesives as referred to above are polymerizable monomers having acid groups in the molecule. These polymerizable monomers which are known, per se, include (meth)acrylate monomers such as those having in the molecule phosphoric acid diester groups ~Japanese Patent L-O-P Publn. No. 113089/1977), phosphoric acid monoester groups (Japanese Patent L-O-P Publn. No.
21607/1983), carboxyl group or acid anhydride groups (Japanese Patent L-O-P Publn. No. 11149/1979) and acid halide groups (Japanese Patent L-O-P Publn. No.
2 5 151-607/1982).
However, even in the adhesives containing such adhesive monomers as mentioned above, a further improvement 2026~17 is desired in that when a dental restorative material (filling material, metal, etc.) is applied to a tooth, a further improved adhesion between the tooth and material is obtained and, moreover, no gap is formed in the marginal gap between the tooth and material thus united.
OBJECT OF THE INVENTION
The present invention has been made in view of the prior art as mentioned above, and an object of the invention is to provide dental adhesives which are excellent in adhesive properties and, in addition thereto, excellent in marginal sealing properties capable of inhibiting the formation of marginal gap between a tooth and a dental restorative material applied thereto.
SUMMARY OF THE INVENTION
The dental adhesives of the present invention are characterized by comprising glyceryl mono(meth)acrylate and a polymerizable monomer having at least one olefinic double ~ 20 bond and capable of copolymerizing with ~ glyceryl mono(meth)acrylate.
The dental adhesives of the invention as illustrated above may be in the form of a mixture containing glyceryl mono(meth)acrylate and a polymerizable monomer having at least one olefinic double bond and capable of copolymerizing with said glyceryl mono(meth)acrylate.
2~26417 The dental adhesives of the invention mentioned above may also be in the form of at least two packs, one ~ ~e containing glyceryl mono(meth)acrylate, and at least thc other containing a polymerizable monomer having at least one olefinic double bond and capable of copolymerizing with said glyceryl mono(meth)acrylate.
DETAILED DESCRIPTION OF THE INVENTION
The dental adhesives of the present invention comprise 0 glyceryl mono(meth)acrylate and a polymerizable monomer copolymerizable with said glyceryl mono(meth)acrylate.
Gyceryl mono(meth)acrylate has two hydroxy groups in the molecule, and therefore the dental adhesives comrising glyceryl mono(meth)acrylate and a polymerizable monomer copolymerizable with said glyceryl mono(meth)acrylate have excellent adhesive properties and excellent marginal sealing properties capable of inhibiting the formation of marginal gap between a tooth and a dental restorative material.
Gyceryl mono(meth)acrylate include as isomers 1,3-dihydroxyisopropyl (meth)acrylate and 2,3-dihydroxypropyl (meth)acrylate, and 2,3-dihydroxypropyl (meth)acrylate is preferred in point of adhesive properties. Usually, methacrylate monomers are used more frequently than acrylate monomers.
The polymerizable monomer used in the invention includes (meth)acrylic acid esters, (meth)acrylamides, ~192~17 maleic acid esters, fumaric acid esters, vinyl esters such as vinyl acetate, styrene and derivatives thereof, and vinyl compounds such as acrylonitrile and acrolein. Of these monomers as exemplified above, particularly preferred 5 are (meth)acrylic acid esters.
Exemplified as (meth)acrylic acid esters are methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2,2-bis [ 4-(3-methacryloyloxy-2-hydroxy-propoxy)phenyl ]
propane (Bis-GMA), trimethylolethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and N,N-dimethylaminoethyl methacrylate.
Further, as the polymerizable monomers preferably used in the invention, there may be mentioned polymerizable acid monomers having at least one acid group selected from the group comprising O O
-P~OH)2 , -Pl-OH -P~ Z)2 O O O O
I I -P-O-P- -P-O-P- O O
p z I I I 1 11 11 11 11 20 1 , OH OH , OH , -C-OH , -C-z and -C-O-c-(in which Z represents halogen, and further the above-mentioned groups do not link to hydroxyl, halogen or 2~26417 P-O-OH ) and at least one olefinic double bond.
As the polymerizable acid monomers as illustrated above, there may be used such compounds as will be exemplified below.
5(i) The compounds having the group -P~OH)2 include those represented by the following formulas.
ll H2C=C-COOt CH2 ~O-P-OH
bH
H2C=C-COOt CH2 ~oO-P-OH
ll H2C=C-COO~CH2~0-P-OH
OH
H2C=C-COO~ CH2~0-P-OH
OH
H2C=C-cOOcH2cH20 ~ OCH2CH20-P-OH
OH
~ 11 H2C=C-COOcH2 ~ CH20-P-OH
OH
C~ H3 Cl H3 H2C=C C~=CH2 OPO(OH)2 CH3 \ O
ll H2C=C-COOCH2--C--CH20- ~P-OH
~ /3 OH
H O
H2C=C ~CH2-P-OH
OH
l ll H2C=C-CNH~ CH2toN-p-oH
OH
H2C=C-COS t CH2~ S-P-OH
OH
o - P-OH
(ii) The compounds having the group I include those represented by the following formulas.
~2~417 H2C=C O
1l A
H2C=C-COOCH2CH20- ~P-O ~) OH
Il A
H2C=C-cOOcH2cH2 OH
ll H2C=C-COOCH2CH20-P--OCH2CH2Br OH
(iii) The compounds having the group -P~ Z)2 include 10 those represented by the following formulas.
ll H2C=C-COO ~ CH2~ O-P-Cl Cl ll H2C=C-CONH~ CH2~P-Br Br H2C=C-cOOcH2cbHcH20 ~ C ~ OCH2CHCH200C - C=CH2 POCI2 CH3 OPOCl2 2~26~17 p z (iv) The compounds having the group I include those represented by the following ~ormulas.
CH3 ~ O H O
H2C=C-COOCH2CH20--P-Cl H2C=C-COOcH2cH20 /2 Cl H2C=C-cOOcH2cHcH20 ~ C ~ OCH2CHCH200C-C=cH2 O=P-Cl O=P-Cl H2C=C-cOOcH2cHcH20 ~ C ~ O-cH2cHcH2ooc-c=cH2 O O
Il 11 -P-O-P-(v) The compounds having the group OH OH include those represented by the following formulas.
H2C=C-COOCH2CH20 -P-O-P- OCH2CH200C-C=CH2 OH OH
H2C=C-COO~ CH2~oO -P-O-P- cH2cH2ooc-c=cH2 OH OH
21~2~417 H2C=C-CONHCH2CH2-P-O-P- CH2CH2NHOC-C=CH2 OH OH
O O
Il 11 -P-O-P-(vi) The compounds having the group OH include that represented by the following formula.
ll ll l H2C=C-COOCH2CH20-P-O-P~OCH2CH200C-C=CH2)2 OH
(vii) The compounds having the group -C-OH include those represented by the following formulas.
H2C=C-COOCH2CH200C ~COOH
COOH
CH
H2C=C-CONH~ CH2 ~ COOH
CH3 ~ COOH H
H2C=C-COO~ CH2toCH H2C=C ~ COOH
CH
H2C=C-COOCH2CH200C ~ô~
--~` COOH
COOH
~2~41~
1 o (viii) The compounds having the group -C-Z include that represented by the following formula.
H2C=C-COOCH2CH200C ~ COCl O O
(IX) The compounds having the group -C-O-C- include those represented by the following formulas.
CH3 C~O
H2C=C-COOCH2CH200C ~ C
H2C=C-COOCH2CH200C ~` C
C_ O
As mentioned above, the dental adhesives of the present invention comprise glyceryl mono(meth)acrylate and a polymerizable monomer, preferably a polymerizable acid monomer capable of copolymerizing with ~aid glyceryl mono(meth)acrylate, and are used usually in the following form.
(1) The dental adhesive used is in the form of a system comprising a mixture of glyceryl mono(meth)acrylate and a polymerizable monomer, preferably a polymerizable 2~2~117 acid monomer capable of copolymerizing with said glyceryl mono(meth)acrylate, or of the above-mentioned system to which a third component such as a solvent, filler or polymerization initiator has been added if necessary.
S In the dental adhesives used in the above-mentioned form, the amount, based on the total weight of the adhesive, of glyceryl mono(meth)acrylate contained is 0.01-50 % by weight, preferably 0.1-30 % by weight, and similarly that of the polymerizable acid monomer contained is 0.01-50 % by weight, preferably 0.1-30 % by weight.
Because of a one-packtype formulation, the dental adhesives mentioned in the foregoing (1) are easy in handling in comparison with the dental adhesives as will be formulated in the undermentioned (2) and have no practical difficulties in respect to their storage stability.
The dental adhesives having the formulation of such mixture as mentioned above are used by applying them on a tooth, especially a dentin.
(2) The dental adhesive used is in the form of a system comprising a package containing a composition [A] in which glyceryl mono(meth)acrylate has been contained and a package containing a composition [B] in which a polymerizable monomer, preferably a polymerizable acid p~
monomer capable of copolymerizing with s-aid glyceryl mono(meth)acrylate has been added.
The dental adhesives having such a formulation as mentioned above are used in such a manner that the 2~6417 composition [A] is first applied on a tooth, especially a dentin, and the composition [B] is laminated by applied on the surface of the composition [A] thus coated.
The composition [A] contains glyceryl mono(meth)-acrylate and a volatile organic solvent having a boilingpoint of below 200 C at atmospheric pressure or water or mixtures thereof and if necessary, copolymerizable monomers, polymerization initiators, fillers, etc. The amount, based on the total weight of the composition [A], 0 of glyceryl mono(meth)acrylate contained therein is 0.1-80 % by weight, preferably 1-50 % by weight, and similarly that of the polymerizable acid monomer contained is 0.01-50 % by weight, preferably 0.1-30 % by weight.
The composition [B] usually contains a polymerization initiator in addition to the above-mentioned polymerizable monomer, and if necessary, may contain a solvent, fillers, etc. Furthermore, the composition [B] may be formulated into a two-divided pack system.
The content in the composition [B] of the above-mentioned polymerizable monomer is 0.01-50 % by weight, preferably 0.1-30 % by weight. The weight proportion of the composition [A] to the composition [B] used in the dental adhesives is from 1:100 to 10:1, preferably from 1:10 to 2:1.
The solvent preferably used in the dental adhesives of the present invention includes volatile organic solvents having boiling point below 200 C at atmospheric pressure, 2i~2~17 for example, alcohols such as methanol, ethanol, allyl alcohol, isopropanol and 1-octanol; ketones such as acetone, methyl ethyl ketone and phorone; ethers such as ethyl ether, 1,4-dioxane, diethylene glycol and diethyl ether; esters such as ethyl acetate, butyl acetate and 2-ethylhexyl acetate; and hydrocarbons such as hexane, undecane, toluene, xylene, methylene chloride, 1,2-dichloroethane and 1,1,2,2-tetrachloroethane, or water or mixtures thereof.
The polymerization initiator used in the dental adhesives of the dental adhesives of the invention includes benzoyl peroxide-aromatic tertiary amine systems, peroxides such as cumene hydroperoxide, tributyl borane, and aromatic sulfinic acid (or salts thereof) -aromatic secondary or tertiary amine-acylperoxide systems, and further includes photopolymerization initiators such as a-diketone (e.g.
camphorquinone, diacetyl or benzyl) -reducing agent systems and benzoin methyl ether, etc.
The filler used in the adhesives of the invention includes inorganic fillers such as glass, quartz, hydroxyapatite, calcium carbonate, barium sulfate, aluminum oxide, titanium oxide and zirconium oxide, and polymer powders such as polymethyl methacrylate, polystyrene and polyvinyl chloride, etc.
The dental adhesives of the invention are used in the same manner as in the case of common dental adhesive.
Namely the present dental adhesives are applied on a tooth, ... ,, . ~
~6~17 and then the dental restorative material such as a filling material, metal or the like is applied to the surface of the thus coated tooth.
EFFECT OF THE INVENTION
The dental adhesives of the present invention have excellent adhesive properties to a tooth, especially dentin and, at the same time, are excellent in properties of marginal sealing between the tooth and the dental restorative material applied thereto. Accordingly, the present dental adhesives are useful for various dental purposes wherein such effects as mentioned above are required, especially for restoring teeth suffering from caries including particularly cervical dentin.
lS The present invention is illustrated below in detail with reference to examples, but it should be construed that the invention is in no way limited to those examples.
Example 1 A composition (A) comprising 35 parts by weight of 2,3-dihydroxypropyl methacrylate ( glyceryl mono(meth)-acrylate ) and 65 parts by weight of water was applied to the flat surface of dentin of an extracted human tooth abraded with #1000 abrasive paper and treated with 0.5 M
aqueous EDTA solution, followed by air blowing. The flat surface of dentin thus applied was further coated with a commercially available dental adhesive [Clearfil New Bond containing 10-methacryloyloxydecyl dihydrogenphosphate (a polymerizable acid monomer), a product of Kuraray Co., Ltd.]
followed by air blowing, and then placed with a commerclally avallable composite resin (Clearfil F II, a product of Kuraray Co., Ltd.) followed by air blowlng. The thus treated tooth was lmmersed ln water at 37C for 24 hours and then sub~ected to tensile bond strength test to obtaln a tenslle bond strength of 153 kg/cm2.
Example 2 In each of 10 extracted human molar teeth, an adamantine ad~acent to a dentln was removed, the dentln thus exposed was then flatted wlth #1000 abraslve paper, and a cyllndrlcal cavlty of 3 mm ln diameter and 1.5 mm in depth was formed on the flatted dentln. The cavlty thus formed was then treated inslde wlth 0.5 M aqueous EDTA solution for 60 seconds, followed by water washing and then drying.
Thereafter, the composition (A) used in Example 1 was applied to the whole lnner wall of the cavlty, followed by alr blowlng. The lnner wall of the cavity was coated with Clearfil New Bond followed by air blowing, and the cavity was filled with Clearfll F II, followed by settlng.
Immedlately thereafter, the tooth thus treated was immersed in water at room temperature, and allowed to stand for 10 mlnutes. Thereafter, the fllled portlon of the cavlty was mlrror pollshed to expose the cavity verge, and an interfacial border between the cavlty verge and the fllling materlals was observed by means of a optlcal microscope * Trade-mark ~`
2026~1~
(NIKON,* OPTIPHOTO X 400) so as to ascertaln whether a gap ls formed or not. As the result, no gap was observed at all over the whole clrcumferentlal verge of all of 10 speclmens, and a good bonded state was shown in every case.
Example 3 Example 2 was repeated except that the cavity was fllled wlth a commerclally avallable composlte resln (PhotoClearfll A, a product of Kuraray Co., Ltd.) ln place of Clearfll F II, and the composite resin was cured by lrradlatlon wlth llght for 40 seconds by means of a vlslble llght lrradlatlon equlpment (QulckLlght manufactured by Kuraray Co., Ltd.), followed by the same test as ln Example 2.
The results obtalned were good, showlng that the speclmens ln whlch no gap was observed at all ln the whole marglnal gap of the cavlty were 9 cases out of 10.
Example 4 Example 2 was repeated except that a composltlon comprlslng 35 parts by welght of 2,3-dlhydroxypropyl methacrylate, 35 parts by welght of water and 30 parts by welght of ethanol was used in place of the composition (A), followed by the same test as in Example 2. The results obtained were good, showing that the specimens in which no gap was observed were 9 cases out of 10.
Example 5 The undermentioned composition (~) was applied to the flat surface of a dentin of extracted human tooth abraded with #1000 abrasive paper and treated with 0.5 M aqueous EDTA
* Trade-mark . ~, j solutlon for 60 seconds, followlng by lrradlation wlth light for 20 seconds by means of a vlsible llght lrradlatlon equlpment (QulckLlght manufactured by Kuraray Co., Ltd.).
Thereafter, the flat surface thus treated was placed with a commerclally avallable photocurlng composlte resln (PhotoClearfil , a product of Kuraray Co., Ltd.), and cured by lrradlatlon wlth llght from QulckLlght for 40 seconds. The thus treated tooth was lmmersed ln water at 37C for 24 hours, and was then sub~ected to tenslle bond strength test to obtaln a tenslle bond strength of 141 kg/cm2.
Composltlon (B) 2,3-Dlhydroxypropyl methacrylate 30 parts by weight Bls-GMA 60 parts by welght 10-Methacryloyloxydecyl dlhydrogen phosphate 10 parts by welght Camphor qulnone 0.5 parts by welght Ethyl N,N-dlmethyl-p-amlnobenzoate 0.5 parts by welght Example 6 Example 3 was repeated except that the composltlon (B) was applled to the cavlty of the speclmens ln place of the composltlon and Clearfll New Bond, followed by the same test as ln Example 3. The results obtained were the same as those obtalned ln Example 3.
Example 7-12 * Trade-mark 2026ql7 Example 3 were repeated except that the undermentioned composition (C) was used in place of Clearfil New Bond, followed by the same test as in Example 3. The results obtained were good as shown in Table 1.
Composition (C) Triethylene glycol dimethacrylate 30 parts by weight Bis-GMA 50 parts by weight Polymerizable acid monomer 20 parts by weight (as disclosed in Table 1) Camphor quinone 0.5 parts by weight Ethyl N,N-dimethyl-p -aminobenzoate 0.5 parts by weight 2026~7 Table 1 Number of Example Polymerizable acid monomer specimens having no qap 7 1 1l CH2=C-COO( CH2~0-P tOH )2 10 8 1 1l CH2=C-COO( CH2~1o~P tCl )2 9 ll ll l 9CH2=C-COOCH2CH20-P-O-P-OCH2CH200C-C=CH2 OH OH g 10CH2=C-COOCH2CH200C ~COOH
11CH2=C-COOCH2CH200C ~
COCI g 12 CH2=C-COOCH2CH200C ~ C \
~C ~o o 10 Comparative Example 1 Example 1 was repeated except that only Clearfil New Bond was applied to the tooth without using the composition (A), followed by the same adhesion test as in Example 1.
S The tensile bond strength as measured was 102 kg/cm2.
Comparative Example 2 Example 2 was repeated except that only Clearfil New Bond was applied to the cavity without using the composition (A), followed by the same test as in Example 2.
0 As the result, the specimens in which no gap was observed at all in the whole marginal gap were 6 cases out of 10.
Comparative Example 3 Example 2 was repeated except that a composition comprising 35 parts by weight of 2-hydroxyethyl lS methacrylate and 65 parts by weight of water was applied to the cavity in place of the composition (A), followed by the same test as in Example 2. As the result, the specimens in which no gap was observed at all were 7 cases out of 10.
Comparative Example 4 Example 5 was repeated except that the composition (B) containing propyl methacrylate in place of the 2,3-dihydroxypropyl methacrylate was used, followed by the same adhesion test as in Example 5. The tensile bond strength as measured was 75 kg/cm2.
2~2~17 Comparative Example 5 Example 6 was repeated except that the composition (B) containing propyl methacrylate in place of the 2,3-dihydroxypropyl methacrylate was used, followed by the same test as in Example 6. As the result, the specimens in which no gap was observed in the whole marginal gap were 4 cases out of 10.
However, even in the adhesives containing such adhesive monomers as mentioned above, a further improvement 2026~17 is desired in that when a dental restorative material (filling material, metal, etc.) is applied to a tooth, a further improved adhesion between the tooth and material is obtained and, moreover, no gap is formed in the marginal gap between the tooth and material thus united.
OBJECT OF THE INVENTION
The present invention has been made in view of the prior art as mentioned above, and an object of the invention is to provide dental adhesives which are excellent in adhesive properties and, in addition thereto, excellent in marginal sealing properties capable of inhibiting the formation of marginal gap between a tooth and a dental restorative material applied thereto.
SUMMARY OF THE INVENTION
The dental adhesives of the present invention are characterized by comprising glyceryl mono(meth)acrylate and a polymerizable monomer having at least one olefinic double ~ 20 bond and capable of copolymerizing with ~ glyceryl mono(meth)acrylate.
The dental adhesives of the invention as illustrated above may be in the form of a mixture containing glyceryl mono(meth)acrylate and a polymerizable monomer having at least one olefinic double bond and capable of copolymerizing with said glyceryl mono(meth)acrylate.
2~26417 The dental adhesives of the invention mentioned above may also be in the form of at least two packs, one ~ ~e containing glyceryl mono(meth)acrylate, and at least thc other containing a polymerizable monomer having at least one olefinic double bond and capable of copolymerizing with said glyceryl mono(meth)acrylate.
DETAILED DESCRIPTION OF THE INVENTION
The dental adhesives of the present invention comprise 0 glyceryl mono(meth)acrylate and a polymerizable monomer copolymerizable with said glyceryl mono(meth)acrylate.
Gyceryl mono(meth)acrylate has two hydroxy groups in the molecule, and therefore the dental adhesives comrising glyceryl mono(meth)acrylate and a polymerizable monomer copolymerizable with said glyceryl mono(meth)acrylate have excellent adhesive properties and excellent marginal sealing properties capable of inhibiting the formation of marginal gap between a tooth and a dental restorative material.
Gyceryl mono(meth)acrylate include as isomers 1,3-dihydroxyisopropyl (meth)acrylate and 2,3-dihydroxypropyl (meth)acrylate, and 2,3-dihydroxypropyl (meth)acrylate is preferred in point of adhesive properties. Usually, methacrylate monomers are used more frequently than acrylate monomers.
The polymerizable monomer used in the invention includes (meth)acrylic acid esters, (meth)acrylamides, ~192~17 maleic acid esters, fumaric acid esters, vinyl esters such as vinyl acetate, styrene and derivatives thereof, and vinyl compounds such as acrylonitrile and acrolein. Of these monomers as exemplified above, particularly preferred 5 are (meth)acrylic acid esters.
Exemplified as (meth)acrylic acid esters are methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2,2-bis [ 4-(3-methacryloyloxy-2-hydroxy-propoxy)phenyl ]
propane (Bis-GMA), trimethylolethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and N,N-dimethylaminoethyl methacrylate.
Further, as the polymerizable monomers preferably used in the invention, there may be mentioned polymerizable acid monomers having at least one acid group selected from the group comprising O O
-P~OH)2 , -Pl-OH -P~ Z)2 O O O O
I I -P-O-P- -P-O-P- O O
p z I I I 1 11 11 11 11 20 1 , OH OH , OH , -C-OH , -C-z and -C-O-c-(in which Z represents halogen, and further the above-mentioned groups do not link to hydroxyl, halogen or 2~26417 P-O-OH ) and at least one olefinic double bond.
As the polymerizable acid monomers as illustrated above, there may be used such compounds as will be exemplified below.
5(i) The compounds having the group -P~OH)2 include those represented by the following formulas.
ll H2C=C-COOt CH2 ~O-P-OH
bH
H2C=C-COOt CH2 ~oO-P-OH
ll H2C=C-COO~CH2~0-P-OH
OH
H2C=C-COO~ CH2~0-P-OH
OH
H2C=C-cOOcH2cH20 ~ OCH2CH20-P-OH
OH
~ 11 H2C=C-COOcH2 ~ CH20-P-OH
OH
C~ H3 Cl H3 H2C=C C~=CH2 OPO(OH)2 CH3 \ O
ll H2C=C-COOCH2--C--CH20- ~P-OH
~ /3 OH
H O
H2C=C ~CH2-P-OH
OH
l ll H2C=C-CNH~ CH2toN-p-oH
OH
H2C=C-COS t CH2~ S-P-OH
OH
o - P-OH
(ii) The compounds having the group I include those represented by the following formulas.
~2~417 H2C=C O
1l A
H2C=C-COOCH2CH20- ~P-O ~) OH
Il A
H2C=C-cOOcH2cH2 OH
ll H2C=C-COOCH2CH20-P--OCH2CH2Br OH
(iii) The compounds having the group -P~ Z)2 include 10 those represented by the following formulas.
ll H2C=C-COO ~ CH2~ O-P-Cl Cl ll H2C=C-CONH~ CH2~P-Br Br H2C=C-cOOcH2cbHcH20 ~ C ~ OCH2CHCH200C - C=CH2 POCI2 CH3 OPOCl2 2~26~17 p z (iv) The compounds having the group I include those represented by the following ~ormulas.
CH3 ~ O H O
H2C=C-COOCH2CH20--P-Cl H2C=C-COOcH2cH20 /2 Cl H2C=C-cOOcH2cHcH20 ~ C ~ OCH2CHCH200C-C=cH2 O=P-Cl O=P-Cl H2C=C-cOOcH2cHcH20 ~ C ~ O-cH2cHcH2ooc-c=cH2 O O
Il 11 -P-O-P-(v) The compounds having the group OH OH include those represented by the following formulas.
H2C=C-COOCH2CH20 -P-O-P- OCH2CH200C-C=CH2 OH OH
H2C=C-COO~ CH2~oO -P-O-P- cH2cH2ooc-c=cH2 OH OH
21~2~417 H2C=C-CONHCH2CH2-P-O-P- CH2CH2NHOC-C=CH2 OH OH
O O
Il 11 -P-O-P-(vi) The compounds having the group OH include that represented by the following formula.
ll ll l H2C=C-COOCH2CH20-P-O-P~OCH2CH200C-C=CH2)2 OH
(vii) The compounds having the group -C-OH include those represented by the following formulas.
H2C=C-COOCH2CH200C ~COOH
COOH
CH
H2C=C-CONH~ CH2 ~ COOH
CH3 ~ COOH H
H2C=C-COO~ CH2toCH H2C=C ~ COOH
CH
H2C=C-COOCH2CH200C ~ô~
--~` COOH
COOH
~2~41~
1 o (viii) The compounds having the group -C-Z include that represented by the following formula.
H2C=C-COOCH2CH200C ~ COCl O O
(IX) The compounds having the group -C-O-C- include those represented by the following formulas.
CH3 C~O
H2C=C-COOCH2CH200C ~ C
H2C=C-COOCH2CH200C ~` C
C_ O
As mentioned above, the dental adhesives of the present invention comprise glyceryl mono(meth)acrylate and a polymerizable monomer, preferably a polymerizable acid monomer capable of copolymerizing with ~aid glyceryl mono(meth)acrylate, and are used usually in the following form.
(1) The dental adhesive used is in the form of a system comprising a mixture of glyceryl mono(meth)acrylate and a polymerizable monomer, preferably a polymerizable 2~2~117 acid monomer capable of copolymerizing with said glyceryl mono(meth)acrylate, or of the above-mentioned system to which a third component such as a solvent, filler or polymerization initiator has been added if necessary.
S In the dental adhesives used in the above-mentioned form, the amount, based on the total weight of the adhesive, of glyceryl mono(meth)acrylate contained is 0.01-50 % by weight, preferably 0.1-30 % by weight, and similarly that of the polymerizable acid monomer contained is 0.01-50 % by weight, preferably 0.1-30 % by weight.
Because of a one-packtype formulation, the dental adhesives mentioned in the foregoing (1) are easy in handling in comparison with the dental adhesives as will be formulated in the undermentioned (2) and have no practical difficulties in respect to their storage stability.
The dental adhesives having the formulation of such mixture as mentioned above are used by applying them on a tooth, especially a dentin.
(2) The dental adhesive used is in the form of a system comprising a package containing a composition [A] in which glyceryl mono(meth)acrylate has been contained and a package containing a composition [B] in which a polymerizable monomer, preferably a polymerizable acid p~
monomer capable of copolymerizing with s-aid glyceryl mono(meth)acrylate has been added.
The dental adhesives having such a formulation as mentioned above are used in such a manner that the 2~6417 composition [A] is first applied on a tooth, especially a dentin, and the composition [B] is laminated by applied on the surface of the composition [A] thus coated.
The composition [A] contains glyceryl mono(meth)-acrylate and a volatile organic solvent having a boilingpoint of below 200 C at atmospheric pressure or water or mixtures thereof and if necessary, copolymerizable monomers, polymerization initiators, fillers, etc. The amount, based on the total weight of the composition [A], 0 of glyceryl mono(meth)acrylate contained therein is 0.1-80 % by weight, preferably 1-50 % by weight, and similarly that of the polymerizable acid monomer contained is 0.01-50 % by weight, preferably 0.1-30 % by weight.
The composition [B] usually contains a polymerization initiator in addition to the above-mentioned polymerizable monomer, and if necessary, may contain a solvent, fillers, etc. Furthermore, the composition [B] may be formulated into a two-divided pack system.
The content in the composition [B] of the above-mentioned polymerizable monomer is 0.01-50 % by weight, preferably 0.1-30 % by weight. The weight proportion of the composition [A] to the composition [B] used in the dental adhesives is from 1:100 to 10:1, preferably from 1:10 to 2:1.
The solvent preferably used in the dental adhesives of the present invention includes volatile organic solvents having boiling point below 200 C at atmospheric pressure, 2i~2~17 for example, alcohols such as methanol, ethanol, allyl alcohol, isopropanol and 1-octanol; ketones such as acetone, methyl ethyl ketone and phorone; ethers such as ethyl ether, 1,4-dioxane, diethylene glycol and diethyl ether; esters such as ethyl acetate, butyl acetate and 2-ethylhexyl acetate; and hydrocarbons such as hexane, undecane, toluene, xylene, methylene chloride, 1,2-dichloroethane and 1,1,2,2-tetrachloroethane, or water or mixtures thereof.
The polymerization initiator used in the dental adhesives of the dental adhesives of the invention includes benzoyl peroxide-aromatic tertiary amine systems, peroxides such as cumene hydroperoxide, tributyl borane, and aromatic sulfinic acid (or salts thereof) -aromatic secondary or tertiary amine-acylperoxide systems, and further includes photopolymerization initiators such as a-diketone (e.g.
camphorquinone, diacetyl or benzyl) -reducing agent systems and benzoin methyl ether, etc.
The filler used in the adhesives of the invention includes inorganic fillers such as glass, quartz, hydroxyapatite, calcium carbonate, barium sulfate, aluminum oxide, titanium oxide and zirconium oxide, and polymer powders such as polymethyl methacrylate, polystyrene and polyvinyl chloride, etc.
The dental adhesives of the invention are used in the same manner as in the case of common dental adhesive.
Namely the present dental adhesives are applied on a tooth, ... ,, . ~
~6~17 and then the dental restorative material such as a filling material, metal or the like is applied to the surface of the thus coated tooth.
EFFECT OF THE INVENTION
The dental adhesives of the present invention have excellent adhesive properties to a tooth, especially dentin and, at the same time, are excellent in properties of marginal sealing between the tooth and the dental restorative material applied thereto. Accordingly, the present dental adhesives are useful for various dental purposes wherein such effects as mentioned above are required, especially for restoring teeth suffering from caries including particularly cervical dentin.
lS The present invention is illustrated below in detail with reference to examples, but it should be construed that the invention is in no way limited to those examples.
Example 1 A composition (A) comprising 35 parts by weight of 2,3-dihydroxypropyl methacrylate ( glyceryl mono(meth)-acrylate ) and 65 parts by weight of water was applied to the flat surface of dentin of an extracted human tooth abraded with #1000 abrasive paper and treated with 0.5 M
aqueous EDTA solution, followed by air blowing. The flat surface of dentin thus applied was further coated with a commercially available dental adhesive [Clearfil New Bond containing 10-methacryloyloxydecyl dihydrogenphosphate (a polymerizable acid monomer), a product of Kuraray Co., Ltd.]
followed by air blowing, and then placed with a commerclally avallable composite resin (Clearfil F II, a product of Kuraray Co., Ltd.) followed by air blowlng. The thus treated tooth was lmmersed ln water at 37C for 24 hours and then sub~ected to tensile bond strength test to obtaln a tenslle bond strength of 153 kg/cm2.
Example 2 In each of 10 extracted human molar teeth, an adamantine ad~acent to a dentln was removed, the dentln thus exposed was then flatted wlth #1000 abraslve paper, and a cyllndrlcal cavlty of 3 mm ln diameter and 1.5 mm in depth was formed on the flatted dentln. The cavlty thus formed was then treated inslde wlth 0.5 M aqueous EDTA solution for 60 seconds, followed by water washing and then drying.
Thereafter, the composition (A) used in Example 1 was applied to the whole lnner wall of the cavlty, followed by alr blowlng. The lnner wall of the cavity was coated with Clearfil New Bond followed by air blowing, and the cavity was filled with Clearfll F II, followed by settlng.
Immedlately thereafter, the tooth thus treated was immersed in water at room temperature, and allowed to stand for 10 mlnutes. Thereafter, the fllled portlon of the cavlty was mlrror pollshed to expose the cavity verge, and an interfacial border between the cavlty verge and the fllling materlals was observed by means of a optlcal microscope * Trade-mark ~`
2026~1~
(NIKON,* OPTIPHOTO X 400) so as to ascertaln whether a gap ls formed or not. As the result, no gap was observed at all over the whole clrcumferentlal verge of all of 10 speclmens, and a good bonded state was shown in every case.
Example 3 Example 2 was repeated except that the cavity was fllled wlth a commerclally avallable composlte resln (PhotoClearfll A, a product of Kuraray Co., Ltd.) ln place of Clearfll F II, and the composite resin was cured by lrradlatlon wlth llght for 40 seconds by means of a vlslble llght lrradlatlon equlpment (QulckLlght manufactured by Kuraray Co., Ltd.), followed by the same test as ln Example 2.
The results obtalned were good, showlng that the speclmens ln whlch no gap was observed at all ln the whole marglnal gap of the cavlty were 9 cases out of 10.
Example 4 Example 2 was repeated except that a composltlon comprlslng 35 parts by welght of 2,3-dlhydroxypropyl methacrylate, 35 parts by welght of water and 30 parts by welght of ethanol was used in place of the composition (A), followed by the same test as in Example 2. The results obtained were good, showing that the specimens in which no gap was observed were 9 cases out of 10.
Example 5 The undermentioned composition (~) was applied to the flat surface of a dentin of extracted human tooth abraded with #1000 abrasive paper and treated with 0.5 M aqueous EDTA
* Trade-mark . ~, j solutlon for 60 seconds, followlng by lrradlation wlth light for 20 seconds by means of a vlsible llght lrradlatlon equlpment (QulckLlght manufactured by Kuraray Co., Ltd.).
Thereafter, the flat surface thus treated was placed with a commerclally avallable photocurlng composlte resln (PhotoClearfil , a product of Kuraray Co., Ltd.), and cured by lrradlatlon wlth llght from QulckLlght for 40 seconds. The thus treated tooth was lmmersed ln water at 37C for 24 hours, and was then sub~ected to tenslle bond strength test to obtaln a tenslle bond strength of 141 kg/cm2.
Composltlon (B) 2,3-Dlhydroxypropyl methacrylate 30 parts by weight Bls-GMA 60 parts by welght 10-Methacryloyloxydecyl dlhydrogen phosphate 10 parts by welght Camphor qulnone 0.5 parts by welght Ethyl N,N-dlmethyl-p-amlnobenzoate 0.5 parts by welght Example 6 Example 3 was repeated except that the composltlon (B) was applled to the cavlty of the speclmens ln place of the composltlon and Clearfll New Bond, followed by the same test as ln Example 3. The results obtained were the same as those obtalned ln Example 3.
Example 7-12 * Trade-mark 2026ql7 Example 3 were repeated except that the undermentioned composition (C) was used in place of Clearfil New Bond, followed by the same test as in Example 3. The results obtained were good as shown in Table 1.
Composition (C) Triethylene glycol dimethacrylate 30 parts by weight Bis-GMA 50 parts by weight Polymerizable acid monomer 20 parts by weight (as disclosed in Table 1) Camphor quinone 0.5 parts by weight Ethyl N,N-dimethyl-p -aminobenzoate 0.5 parts by weight 2026~7 Table 1 Number of Example Polymerizable acid monomer specimens having no qap 7 1 1l CH2=C-COO( CH2~0-P tOH )2 10 8 1 1l CH2=C-COO( CH2~1o~P tCl )2 9 ll ll l 9CH2=C-COOCH2CH20-P-O-P-OCH2CH200C-C=CH2 OH OH g 10CH2=C-COOCH2CH200C ~COOH
11CH2=C-COOCH2CH200C ~
COCI g 12 CH2=C-COOCH2CH200C ~ C \
~C ~o o 10 Comparative Example 1 Example 1 was repeated except that only Clearfil New Bond was applied to the tooth without using the composition (A), followed by the same adhesion test as in Example 1.
S The tensile bond strength as measured was 102 kg/cm2.
Comparative Example 2 Example 2 was repeated except that only Clearfil New Bond was applied to the cavity without using the composition (A), followed by the same test as in Example 2.
0 As the result, the specimens in which no gap was observed at all in the whole marginal gap were 6 cases out of 10.
Comparative Example 3 Example 2 was repeated except that a composition comprising 35 parts by weight of 2-hydroxyethyl lS methacrylate and 65 parts by weight of water was applied to the cavity in place of the composition (A), followed by the same test as in Example 2. As the result, the specimens in which no gap was observed at all were 7 cases out of 10.
Comparative Example 4 Example 5 was repeated except that the composition (B) containing propyl methacrylate in place of the 2,3-dihydroxypropyl methacrylate was used, followed by the same adhesion test as in Example 5. The tensile bond strength as measured was 75 kg/cm2.
2~2~17 Comparative Example 5 Example 6 was repeated except that the composition (B) containing propyl methacrylate in place of the 2,3-dihydroxypropyl methacrylate was used, followed by the same test as in Example 6. As the result, the specimens in which no gap was observed in the whole marginal gap were 4 cases out of 10.
Claims (10)
1. A dental adhesive comprising glyceryl mono(meth)-acrylate and a polymerizable monomer having at least one olefinic double bond and capable of coplymerizing with said glyceryl monotmeth)acrylate.
2. The dental adhesive as claimed in claim 1 wherein said adhesive is in the form of a mixture of glyceryl mono(meth)acrylate and a polymerizable monomer having at least one olefinic double bond and capable of copolymerizing with said glyceryl mono(meth)acrylate.
3. A dental adhesive as claimed in claim 1 wherein said adhesive is in the form of at least two packs, one containing glyceryl mono(meth)acrylate, and at least one other containing a polymerizable monomer having at least one olefinic double bond and capable of copolymerizing with said glyceryl mono(meth)acrylate.
4. The dental adhesive as claimed in claim 2 or 3 wherein glyceryl mono(meth)acrylate is dissolved in a volatile organic solvent having a boiling point of below 200 °C at atmospheric pressure, water or a mixture thereof.
5. The dental adhesive as claimed in any one of claim 1-3 wherein polymerizable monomer capable of copolymerizing with glyceryl mono(meth)acrylate is a polymerizable acid monomer having at least one acid qroup selected from the group comprising , , , , , , , and (in which Z represents halogen, and further the above-mentioned groups do not link to hydroxyl, halogen or and at least one olefinic double bond.
6. A dental adhesive for bonding a tooth and a dental restorative material together, which comprises:
(i) glyceryl mono(meth)acrylate in an amount of 0.01 to 50% by weight of the dental adhesive, (ii) a polymerizable monomer having at least one olefinic double bond and being capable of copolymerizing with the glyceryl mono(meth)acrylate in an amount of 0.01 to 50% by weight of the dental adhesive, and (iii) from 0% to the balance of the dental adhesive being at least one member selected from the group consisting of a solvent, a filler and a polymerization initiator, wherein the polymerizable monomer is selected from the group consisting of:
[1] an ester of (meth)acrylic acid other than glyceryl mono(meth)acrylate, an ester of maleic acid, an ester of fumaric acid, vinyl acetate, styrene, acrylonitrile or acrolein, and [2] a polymerizable acid monomer having at least one acid group of the formula:
, , , , , , , or (wherein Z represents halogen) and at least one olefinic double bond, with the proviso that the acid group of the formula is not linked to a hydroxyl, halogen or -P(O)(OH)-O-; and the adhesive is in the form a mixture containing the glyceryl mono(meth)acrylate (i) and the polymerizable monomer (ii) but not containing a polymerization initiator or the adhesive is in the form of at least two packs, one containing the glyceryl mono(meth)acrylate and at least one other containing the polymerizable monomer.
(i) glyceryl mono(meth)acrylate in an amount of 0.01 to 50% by weight of the dental adhesive, (ii) a polymerizable monomer having at least one olefinic double bond and being capable of copolymerizing with the glyceryl mono(meth)acrylate in an amount of 0.01 to 50% by weight of the dental adhesive, and (iii) from 0% to the balance of the dental adhesive being at least one member selected from the group consisting of a solvent, a filler and a polymerization initiator, wherein the polymerizable monomer is selected from the group consisting of:
[1] an ester of (meth)acrylic acid other than glyceryl mono(meth)acrylate, an ester of maleic acid, an ester of fumaric acid, vinyl acetate, styrene, acrylonitrile or acrolein, and [2] a polymerizable acid monomer having at least one acid group of the formula:
, , , , , , , or (wherein Z represents halogen) and at least one olefinic double bond, with the proviso that the acid group of the formula is not linked to a hydroxyl, halogen or -P(O)(OH)-O-; and the adhesive is in the form a mixture containing the glyceryl mono(meth)acrylate (i) and the polymerizable monomer (ii) but not containing a polymerization initiator or the adhesive is in the form of at least two packs, one containing the glyceryl mono(meth)acrylate and at least one other containing the polymerizable monomer.
7. The dental adhesive according to claim 6, wherein the polymerizable monomer comprises a polymerizable phosphoric acid monomer of the formula:
(wherein R1 is H or CH3, R2 is -COO(CH2)nO- , , , , , , -CONH?CH2?NH- or -COS?CH2?S- , and n is an integer of 2 to 20).
(wherein R1 is H or CH3, R2 is -COO(CH2)nO- , , , , , , -CONH?CH2?NH- or -COS?CH2?S- , and n is an integer of 2 to 20).
8. The dental adhesive according to claim 6, wherein the polymerizable monomer comprises an ester of (meth)acrylic acid selected from the group consisting of methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)-phenyl]propane, trimethylolethane tri(meth)acrylate, penta-erythritol tetra(meth)acrylate and dimethylaminoethyl meth-acrylate.
9. The dental adhesive according to claim 6, wherein the polymerizable monomer comprises a polymerizable acid monomer of the formula:
, , , , or .
, , , , or .
10. The dental adhesive according to any one of claims 1 to 3, wherein the glyceryl mono(meth)acrylate is 2,3-dihydroxy-propyl methacrylate.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP81769/1990 | 1990-03-28 | ||
| JP2081769A JPH03279308A (en) | 1990-03-28 | 1990-03-28 | Dental adhesive |
| JP2081768A JP2782694B2 (en) | 1990-03-28 | 1990-03-28 | Dental adhesive |
| JP81768/1990 | 1990-03-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2026417A1 CA2026417A1 (en) | 1991-09-29 |
| CA2026417C true CA2026417C (en) | 1996-07-02 |
Family
ID=26422781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002026417A Expired - Lifetime CA2026417C (en) | 1990-03-28 | 1990-09-27 | Dental adhesives |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2026417C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5876210A (en) | 1994-04-22 | 1999-03-02 | Dentsply G.M.B.H. | Dental polymer product |
| US5932627A (en) | 1994-05-12 | 1999-08-03 | Dentsply Gmbh | Fluoride releasing dental primer composition and method |
| US5998499A (en) | 1994-03-25 | 1999-12-07 | Dentsply G.M.B.H. | Liquid crystalline (meth)acrylate compounds, composition and method |
| US6353061B1 (en) | 1993-05-26 | 2002-03-05 | Dentsply Gmbh | α, ω-methacrylate terminated macromonomer compounds |
| US6369164B1 (en) | 1993-05-26 | 2002-04-09 | Dentsply G.M.B.H. | Polymerizable compounds and compositions |
-
1990
- 1990-09-27 CA CA002026417A patent/CA2026417C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6339114B1 (en) | 1993-05-26 | 2002-01-15 | Dentsply Detrey Gmbh | Liquid crystalline (meth)acrylate compounds, composition and method |
| US6353061B1 (en) | 1993-05-26 | 2002-03-05 | Dentsply Gmbh | α, ω-methacrylate terminated macromonomer compounds |
| US6369164B1 (en) | 1993-05-26 | 2002-04-09 | Dentsply G.M.B.H. | Polymerizable compounds and compositions |
| US5998499A (en) | 1994-03-25 | 1999-12-07 | Dentsply G.M.B.H. | Liquid crystalline (meth)acrylate compounds, composition and method |
| US5876210A (en) | 1994-04-22 | 1999-03-02 | Dentsply G.M.B.H. | Dental polymer product |
| US5932627A (en) | 1994-05-12 | 1999-08-03 | Dentsply Gmbh | Fluoride releasing dental primer composition and method |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2026417A1 (en) | 1991-09-29 |
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