CN101588782B - Adhesive composition for dental use - Google Patents
Adhesive composition for dental use Download PDFInfo
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- CN101588782B CN101588782B CN2007800503155A CN200780050315A CN101588782B CN 101588782 B CN101588782 B CN 101588782B CN 2007800503155 A CN2007800503155 A CN 2007800503155A CN 200780050315 A CN200780050315 A CN 200780050315A CN 101588782 B CN101588782 B CN 101588782B
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Abstract
Disclosed is an adhesive composition for dental use, which comprises a polymerizable monomer component (A) comprising a phosphoric acid-type polymerizable monomer having an acidic group derived from phosphoric acid and a multivalent metal ion-releasing component (B) and shows an acidic nature, wherein the multivalent metal ion-releasing component (B) can release at least an earth metal ion, and wherein an earth metal ion derived from the component (B) is present in the composition together with the phosphoric acid-type polymerizable monomer in such an amount that a ratio of total valency number (RE) as defined by the formula (1) is 0.2 to 3.0. RE = TVE/TVA (1) [wherein TVE represents the total number of valencies of the earth metal ions contained in the composition; and TVA represents thetotal number of valencies of the acidic group in the phosphoric acid-type polymerizable monomer contained in the composition.] The adhesive composition can adhere and fix a composite resin or prosthesis to a tooth structure more tightly and stably over a prolonged period.
Description
Technical field
The present invention relates in the dental care field, be used for the dental prosthesis and the adherent adhesive composition for dental use of dentine that constitute by metal, organic polymer, pottery or their composite etc.
Background technology
In dentine because under the situation that dental caries erosion etc. sustains damage, since the nest hole that damage causes hour, from the simplicity of taste, operation and the viewpoint of rapidity, the situation of directly repairing with composite resin is more.On the other hand, because the damage nest hole of causing when big, uses the prosthesis of being made by metal, pottery or resin cured matter to repair the nest hole.
Because dental prosthetic materials such as composite resin or prosthesis do not have cohesive to dentine, therefore use the jointing material that forms by polymerizable composition, polymerizable composition that repair materials and dentine is bonding.The polymerizable composition, polymerizable composition that uses as this jointing material contains the methacrylate ester monomer usually as the main constituent polymerizable monomer, but its bonding force to dentine is insufficient.For example, for composite resin and dentine is bonding and when using polymerizable composition, polymerizable composition, the bonding strength of usually defeating the internal stress (in the tensile stress of the interface of dentine and composite resin generation) that clothes produce continuously when this composite resin solidifies can not obtain.In addition, can not reach tolerance usually because the bonding strength of the power that interlock produces.
Therefore, in order to improve the bonding strength of jointing material, in use, the flank of tooth is carried out following pretreatment:
(a) hard dentine (mainly being to be the enamel of main constituent with the hydroxyapatite) is carried out etch processes, in addition
The cohesive that (b) will be called priming paint (primer) improves composition and is infiltrated up in the dentine.
Here,, the aqueous acid of dental surface deliming is used always, can be used the aqueous solution of phosphoric acid, citric acid, maleic acid etc. as the material previously treated that etch processes is used.
In addition; In etch processes (deliming) afterwards; The enamel of roughening and the dentin that is made up of spongiform collagen fiber owing to the deliming of aqueous acid are exposed in the dentine surface, in order to ensure sufficient bonding strength, and need infiltrate from the surface of this dentine bonding composition and curing.Therefore, as being used for the priming paint that above-mentioned infiltration is handled, can using comprising hydroxyethyl methacrylate (HEMA) etc. to the affinity good hydrophilicity monomer of above-mentioned dentine and the polymerizable monomer composition of organic solvent.In addition, this priming paint itself does not contain polymerization initiator usually, but coating composite resin on it is during with the photocuring reaction of jointing material, through the effect of the free radical that in this jointing material, produces, the polymerizable monomer polymerizing curable in this priming paint.
When carrying out aforesaid pretreatment,, the various dental jointing material compositionss that dentine had fusible polymerizable monomer that contain have been developed in order to obtain higher bonding strength and the trouble that alleviates pretreatment operation.
For example, in patent documentation 1 and patent documentation 2, proposed to comprise and contain the acidic groups polymerizable monomer and use the jointing material compositions as the tooth section of at least a portion of polymerizable monomer composition.In this jointing material compositions, the acidic groups polymerizable monomer that contains that in molecule, has acidic-groups such as phosphate group, hydroxy-acid group has high affinity to dentine (hydroxyapatite and ossein), so it has showed high bonding strength.
In addition; In patent documentation 3～6; Proposed to contain the jointing material compositions of acidic groups polymerizable monomer and water coexistence, this jointing material compositions possesses the deliming function of aqueous acid simultaneously through the effect of acidic-group and the infiltration of priming paint promotes function, thereby does not need to be coated with separately pretreating agent; Can only use once coating operation, the jointing material (one step type jointing material) excellent as operability is favourable.In addition, can also utilize above-mentioned etching and permeability, this adhesive composition that contains the acidic groups polymerizable monomer that comprises is used as the self etching priming paint (for example with reference to patent documentation 8 and patent documentation 9) that has these two kinds of functions concurrently.
Reported in the patent documentation 10 through using having phosphate group and can further improving its bonding strength of calcium salt forms as the polymerizable monomer of acidic-group.
In above-mentioned various prior aries, patent documentation 4～7 has also proposed the scheme of mixed soil metal ion stripping property filler in jointing material that contains acidic groups polymerizable monomer and water and self etching priming paint.The earth metal ion stripping property filler here is meant that the filler of stripping metal ion under the acid solution effect such as aluminum fluoride glass as the metal ion of stripping from this filler, can be enumerated alkaline-earth metal, aluminum etc.This bonding strength that contains the jointing material compositions of earth metal ion stripping property filler further improves; Infer its former because; The polymerization that comprises the polymerizable monomer composition that contains the acidic groups polymerizable monomer has caused curing; And the polyvalent metal ion of stripping and the above-mentioned acidic-group that contains the acidic groups polymerizable monomer produce ionomer from earth metal ion stripping property filler, thereby make the intensity of gained firming body improve.
Patent documentation 1: japanese kokai publication sho 52-113089 communique
Patent documentation 2: japanese kokai publication sho 58-21687 communique
Patent documentation 3: TOHKEMY 2004-352698 communique
Patent documentation 4: japanese kokai publication hei 9-263604 communique
Patent documentation 5: japanese kokai publication hei 10-236912 communique
Patent documentation 6: TOHKEMY 2001-72523 communique
Patent documentation 7: TOHKEMY 2000-86421 communique
Patent documentation 8: japanese kokai publication hei 7-82115 communique
Patent documentation 9: TOHKEMY 2000-159621 communique
Patent documentation 10: japanese kokai publication sho 53-113843 communique
Summary of the invention
The adhesive composition such as jointing material, priming paint that contains the acidic groups polymerizable monomer with do not contain this monomer combination and compare and obtained higher bonding strength; Has the deliming function in addition; Therefore not needing etch processes, can realize the easy of bonding operation, is useful therefore.Yet, owing between dentine and dental restoration, require very high bonding strength, so this bonding strength is still insufficient, so seek to play consistently the more material of high adherence.
In addition, in above-mentioned known adhesive composition, though be combined with the calcium salt of phosphorous acidic group polymerizable monomer or the compositions of earth metal ion stripping property filler is brought up to higher level with bonding strength, this bonding strength remains not enough.
So the inventor etc. have carried out many experiments and research to containing the acidic groups polymerizable monomer with the adhesive composition that earth metal ion stripping property filler cooperates, the result infers the effect that increases that can not give full play to bonding strength from following reason.
For example, in above-mentioned prior art,, use to have with acid reaction and as the chemical compounds such as boric acid allyl ester compound of radical initiator performance function as the polymerization initiator that is matched with in the jointing material.Therefore; As disclosed in the patent documentation 5; In containing the adhesive composition of polymerization initiator; Consider storage stability, will contain the composition of acidic groups polymerizable monomer and water and contain and acid (containing the acidic groups polymerizable monomer) reaction and the composition that produces the polymerization initiator of free radical are filled in another packing and preserve.And; In this preservation form; Commonly, earth metal ion stripping property filler is matched with in the middle of in the packing that is filled with the composition that contains polymerization initiator, with earth metal ion stripping property filler with contain the acidic groups polymerizable monomer assign to another the packing in.Also open in its patent documentation 6, this be for fear of since from the polyvalent metal ion of earth metal ion stripping property filler stripping with contain increase in time and the tackify that ionic bond that the acidic groups polymerizable monomer forms causes compositions.
Under the situation of as stated constituent separately being preserved in two packings, mix the activity duration that begins to institute's liquid mixture prepared being coated till the flank of tooth and be merely several minutes utmost point short time being filled in two compositions in the packing.Therefore, in the earth metal ion stripping property filler also unhappy to the dissolution velocity of aqueous acid, the amount of the polyvalent metal ion of stripping is considerably less in this short time.Therefore, the effect (acidic-group forms ionomer with polyvalent metal ion) of the raising bonding force that produces from the polyvalent metal ion of earth metal ion stripping property filler stripping can not effectively be brought into play, thereby can not give full play to the effect of raising bonding force.
For example; In above-mentioned patent documentation 4, it is after the liquid that each constituent is in harmonious proportion, and former state supplies in adhesive test at once and estimates the bonding force of compositions; But because the earth metal ion stripping property dissolution of fillers time is the short time; When solidifying, can not form sufficient ionomer, improve, not show significant bonding force and improve though observed bonding force to a certain degree.
In addition, in the adhesive composition that is combined with earth metal ion stripping property filler, in order to show sufficient ionomer and to obtain high bonding strength, the kind of the metal ion of stripping also is very important with amount from earth metal ion stripping property filler.For example; When the metal ion of institute's stripping mainly was bivalent metal ions such as univalent metal ion, calcium ion etc., can not obtain sufficient cohesive improved effect, in addition; When the amount of the metal ion of institute's stripping excessively increased, the resistance to water of firming body significantly reduced.That is, even after just solidifying, obtaining in the situation of quite high bonding force, during in the reparation position of tooth, bonding force can reduce gradually in long-term existence, and the result takes place by coming off of dental prosthetic thing etc. easily.
Therefore; The objective of the invention is to; The adhesive composition for dental use that contains the acidic groups polymerizable monomer is provided, and this adhesive composition for dental use can further improve cohesive and durability, and can be more firmly with stably keep the bonding of composite resin or prosthesis and dentine for a long time.
Discoveries such as the inventor; Contain in the acidic groups polymerizable monomer various; Especially have by phosphoric acid in the adhesive composition for dental use of deutero-group as the polymerizable monomer of acidic-group containing; Through the earth metal ion is coexisted as in this liquid with specified quantitative, can address the above problem, thereby accomplish the present invention.
According to the present invention; A kind of adhesive composition for dental use is provided; Said compositions is to be that the polymerizable monomer composition (A) of polymerizable monomer mixes the tart adhesive composition for dental use that appears that obtains with polyvalent metal ion release property composition (B) through containing phosphoric acid; Said phosphoric acid is that polymerizable monomer has by the deutero-acidic-group of phosphoric acid, it is characterized in that
Said polyvalent metal ion release property composition (B) can discharge the earth metal ion at least,
The earth metal ion and the phosphoric acid that come from said composition (B) are that polymerizable monomer is present in the said composition jointly, and with total valence mumber of following formula (1) definition than (R
E) in 0.2～3.0 scope:
R
E＝TV
E/TV
A...(1)
In the formula, TV
EBe the ionic total valence mumber of earth metal that contains in the said composition, TV
ABe that the phosphoric acid that contains in the said composition is total valence mumber of the acidic-group of polymerizable monomer.
In addition, in the present invention, earth metal is to belong to the IIIB family of the periodic table of elements and the metal of group III A.
In adhesive composition for dental use of the present invention, it is desirable to have feature:
(1) said earth metal is aluminum and/or lanthanum,
(2) said composition (B) is an earth metal ion stripping property filler,
(3) said composition (B) is acid and the carbonate of earth metal, rudimentary alkoxide or the hydroxide of carbon number below 4 of earth metal,
(4) to contain the above phosphoric acid of 5 quality % be polymerizable monomer to said polymerizable monomer composition,
(5) said phosphoric acid is that polymerizable monomer is the chemical compound with biphosphate monoesters group and/or phosphoric acid hydrogen two ester groups,
(6) further contain water (C),
(7) further contain aerosil (fumed silica) (D),
(8) further contain polymerization initiator (E).
In addition, representing that said total valence mumber is than (R
E) formula in, the phosphoric acid that contains in the adhesive composition is total valence mumber (TV of the acidic-group of polymerizable monomer (phosphoric acid is monomer)
A) calculate by following formula (1a):
TV
A＝∑P
k×A
k...(1a)
In the formula, k is 1,2,3..., n, and n is that the phosphoric acid that contains in the compositions is the number of monomeric kind,
P
kBe that each phosphoric acid that contains in the said composition is monomeric molal quantity,
A
kBe that each phosphoric acid is the valence mumber of the acidic-group that has of monomer.
For example, be monomer when being biphosphate list (2-methylacryoyloxyethyl) ester at phosphoric acid, the valence mumber of acidic-group is a divalent, is monomer when being phosphoric acid hydrogen two (2-methylacryoyloxyethyl) ester at phosphoric acid, the valence mumber of acidic-group is 1 valency.In addition, the phosphoric acid that contains in the compositions is that monomer is (for example, when only containing the phosphoric acid that only has monovalence acidic-group or bivalence acidic-group and be monomer) under a kind of situation, and according to following formula, this phosphoric acid is that the valence mumber that monomer is calculated becomes total valence mumber (TV
A), and when in said composition, containing multiple phosphoric acid and being monomer, calculating each phosphoric acid is monomeric valence mumber, their sum total is total valence mumber (TV
A).
On the other hand, because the ionic valence mumber of earth metal is 3, so the ionic total valence mumber (TV of the earth metal that contains in the said composition
E) calculate through following formula (1b):
TV
E＝3M
E...(1b)
In the formula, M
EIt is the ionic molal quantity of earth metal that contains in the said composition.
Ionic kind of the earth metal that exists in the adhesive composition for dental use of the present invention and content can be obtained through after removing solid constituent, measuring with inductively coupled plasma (ICP) emission spectrographic analysis device.For example, using water-miscible organic solvent that adhesive composition is diluted to concentration is 1 quality %, with the filtration of gained diluent, removes solid constituent with syringe-type filter etc.Then, measure ionic species and the ion concentration that gained is filtrated, calculate earth metal ionic species and amount in the adhesive composition with ICP emission spectrographic analysis device.
In addition, species of metal ion except the earth metal ion and content thereof the mensuration that also can use the same method.
In addition; Phosphoric acid in the adhesive composition for dental use is that the kind and the content of the acidic-group that had of polymerizable monomer (phosphoric acid is monomer) can be measured as follows: from compositions, isolating phosphoric acid through preparative high performance liquid chromatography is monomer; By isolating phosphoric acid is that its molecular weight is measured in monomeric mass spectral analysis; Decide structure through nuclear magnetic resoance spectrum (NMR) in addition, identify acidic-group and calculate content.
For example, through measuring
31The NMR of P can identify the kind by the deutero-acidic-group of phosphoric acid by its chemical displacement value.That is to say, use the known compound have by the deutero-acidic-group of phosphoric acid, measure these standard substances down at the same terms (retarder thinner, concentration, temperature) as standard substance
31P-NMR and measures adhesive composition
31P-NMR relatively can confirm chemical displacement value.Wherein, be monomeric standard substance as having the phosphoric acid of phosphinic acid base as acidic-group, use the dimethyl phosphinic acid; As the phosphoric acid with phosphonate group is monomeric standard substance; Using methylphosphonic acid, is monomeric standard substance as the phosphoric acid with phosphonic acids hydrogen monoesters base in addition, uses methylphosphonic acid hydrogen mono ethyl ester; As the phosphoric acid with biphosphate monoesters base is monomeric standard substance; Using the biphosphate mono-methyl, is monomeric standard substance as the phosphoric acid with phosphoric acid hydrogen two ester groups, uses phosphoric acid hydrogen dimethylamino ester.
In addition; By being the calibration curve of monomer production standard material through the isolating phosphoric acid of preparative high performance liquid chromatography; In the part of above-mentioned filtrating, add internal standard substance matter, through using high effective liquid chromatography for measuring, the phosphoric acid that can obtain in the compositions is monomeric amount.
Adhesive composition for dental use of the present invention is suitable for using pretreating agent as dental jointing material or dentine.
According to the present invention, the manufacturing approach of adhesive composition for dental use also is provided, it is characterized in that:
With (A), (B) and (C) uniform mixing:
(A) comprise that to have by the phosphoric acid of the deutero-acidic-group of phosphoric acid be the polymerizable monomer composition of polymerizable monomer;
(B) can discharge the ionic polyvalent metal ion release property of earth metal composition at least; And
(C) water,
Then, with this mixture ripening, make total valence mumber that the ionic amount of earth metal that discharged by said composition (B) in the gained mixture defines with following formula (1) than (R
E) in 0.2～3.0 scope:
R
E＝TV
E/TV
A...(1)
In the formula, TV
EBe the ionic total valence mumber of earth metal that contains in the said composition, TV
ABe that the phosphoric acid that contains in the said composition is total valence mumber of the acidic-group of polymerizable monomer.
In adhesive composition for dental use of the present invention, in various polyvalent metal ions, the earth metal ion with total valence mumber than (R
E) to be that polymerizable monomer (phosphoric acid is monomer) is common exist for amount and phosphoric acid in 0.2～3.0 scope, therefore thinks that earth metal ion and phosphoric acid are the acidic-group ionic bonding that monomer has, the ionomer of formation sufficient quantity during curing.As a result, through ionomer and the solidified synergism of polymerizable monomer, can be to the very high bonding strength of dentine (being not limited to dentin and enamel) performance.Therefore; When being used as the jointing material of dental prosthetic thing and dentine; Said composition can have the bonding strength that is enough to resist the tensile stress that produces at the interface of restoration such as composite resin and dentine; In addition, the dental prosthetic thing is after predetermined position is fixing, and it has is enough to resist because the bonding strength of the power that interlock takes place.
In the present invention, be the reason that the monomer coexistence obtains high bonding strength through earth metal ion and the phosphoric acid that makes this specified quantitative, may not be fully clear and definite, but infer through following being used for and realize.
That is to say, be when having metal ion in the monomeric system containing phosphoric acid, and phosphoric acid is monomeric acidic-group and this metal ion ionic bonding, when metal ion is multivalence, produces ionomer.When the polymerizable monomer polyreaction, this ionomer fully takes place and forms, and this has synergism for the generation by the bonding force that polymerizing curable brought, thereby improves its intensity.According to thinking that in the present invention, when in various multivalent ions, having earth metal ion (its valence mumber is 3) jointly, this ionomer fully takes place, and can obtain high bonding strength.For example, divalent metal ion such as calcium ion can not fully carry out ionomer because its valence mumber is little.Think that in addition in the polyvalent metal ion more than 3 valencys, especially the earth metal ion is with high by the ionomer property of the deutero-acidic-group of phosphoric acid; Therefore; Through being monomer and earth metal ion coexist with phosphoric acid, ionomer fully takes place, thereby has showed high bonding strength.
In addition, be that the ionic amount of earth metal of monomer coexistence need make total valence mumber of representing with following formula than (R with phosphoric acid
E) in preset range.That is to say; The ionic part of the earth metal that in compositions, exists and phosphoric acid are that monomer carries out ionomer; Be not that all earth metal ions all form ionomer; In order fully to carry out ionomer, be the acidic-group that monomer has with respect to phosphoric acid, need exist earth metal to reach certain balance.Therefore, in the present invention, total valence mumber is than (R
E) be set in the scope of preset range (0.2～3.0).For example, the ionic amount of earth metal of coexistence than phosphoric acid be that monomer lacks, total valence mumber is than (R
E) than above-mentioned scope hour, certainly, becoming of ionomer is insufficient, does not show the high bonding strength of target.In addition, the ionic amount of earth metal than phosphoric acid be monomer Duo and total valence mumber than (R
E) when bigger than above-mentioned scope, because the amount of acidic-group is few, becoming of ionomer is insufficient, in addition; Gelation etc. takes place easily, and phosphoric acid is that monomeric de-ashing reduces, and still can not show high bonding strength; In addition, even show high bonding strength, it is unsatisfactory that the resistance to water of firming body also becomes; Bonding strength takes place within a short period of time reduce, it is unsatisfactory that adhesion durability becomes, thereby be not suitable for the purposes of dental field.
Like this, in the present invention, needing to regulate the earth metal ion is monomeric amount with respect to phosphoric acid, makes total valence mumber than (R
E) in 0.2～3.0 scope.This total valence mumber is than (R
E) preferably be adjusted in 0.3～0.9 the scope, most preferably be adjusted in 0.4～0.7 the scope.
In addition, adhesive composition for dental use of the present invention presents acidity, therefore has dentine deliming ability concurrently, therefore, even do not carry out etching operation, also can realize high bonding strength.
This adhesive composition for dental use of the present invention has not only shown high bonding strength, and resistance to water is also excellent, even in having the oral cavity of moisture, under the long-term situation about keeping, also stably shown high bonding strength.Therefore; Said composition can be used as can be with dental prosthetic thing and the adherent jointing materials of dentine such as composite resin, prosthesiss; In addition, with dental prosthetic thing and dentine when bonding, can be as using the material previously treated that on the flank of tooth, is coated with before the jointing material.
The specific embodiment
Adhesive composition for dental use of the present invention presents acidity; Through being mixed, (A) polymerizable monomer composition and (B) polyvalent metal ion release property composition obtain; Usually contain the water (C) that is useful on from composition (B) release metal ions; As required, further cooperate aerosil (D), polymerization initiator (E) etc.In addition; Said composition contain as above-mentioned polymerizable monomer composition (A) contain the acidic groups polymerizable monomer, therefore present acidity, but acidity reduces according to the amount of the metal ion that discharges from composition (B); In this case, the acidic materials that are used to regulate pH through cooperation can be regulated acidity.In addition, in said composition, can cooperate known various compounding ingredients in the dental field.
< polymerizable monomer composition (A) >
In the present invention; Polymerizable monomer composition (A) (being designated hereinafter simply as " monomer component ") thus be to give the composition that cohesive is used to composite resin, various prosthesiss etc. in order to solidify through polymerization; For with after the earth metal ion that discharges from composition (B) stated form ionomer, need contain phosphoric acid is polymerizable monomer (A1).
Phosphoric acid is that polymerizable monomer (A1) (hereinafter referred to as phosphoric acid is monomer) is to contain the polymerism unsaturated group in the molecule and by the chemical compound of the deutero-acidic-group of phosphoric acid.
As above-mentioned polymerism unsaturated group, can enumerate acryloyl group, methacryl, acrylamido, methacryl amido, vinyl, pi-allyl, acetenyl, styryl etc.Especially, from the viewpoint of curing rate, acryloyl group, methacryl, acrylamido, methacryl amido are preferred, and acryloyl group and methacryl are most preferred.
In addition, be to have usefulness＞P (=O) group of the structure represented of OH specifically, can be enumerated phosphinic acid base, phosphonate group, phosphonic acids hydrogen monoesters base, biphosphate monoesters base, phosphoric acid hydrogen two ester groups etc. by the deutero-acidic-group of phosphoric acid.In the middle of these, from the infiltrative viewpoint dentine, biphosphate monoesters base [O-P (=O) (OH)
2], phosphoric acid hydrogen two ester groups [(O-)
2P (=O) OH] etc. the phosphoric acid ester group be preferred.This not only the de-ashing of dentine is high by the deutero-acidic-group of phosphoric acid, and also high to the original adhesion of composite resin and dentine, in addition, with after state also excellence of ability that the earth metal ion forms ionomer, especially obtained high bonding strength.
As containing the instantiation that this phosphate ester is the phosphorus acid monomer of group, can enumerate following chemical compound.
Wherein, in above-claimed cpd, R
1Expression hydrogen atom or methyl.
It is a kind of that above-mentioned phosphoric acid is that monomer (A1) can use separately, perhaps can be with two or more and use.
In addition, as the material that phosphoric acid is monomer (A1) that is suitable for beyond above-mentioned, can enumerate following chemical compound.
Phosphoric acid with phosphinic acid base is monomer:
Two (2-methacryloxy) phosphonic acids
Two (methacryloxypropyl) phosphinic acid
Two (methacryl oxygen-butyl) phosphinic acid.
Phosphoric acid with phosphonate group is monomer:
3-methacryloxypropyl phosphonic acids
2-methacryloxy ethoxy carbonyl methylphosphonic acid
4-methacryloxy butoxy carbonyl methyl phosphonic acids
6-methacryloxy hexyloxy carbonyl methylphosphonic acid
2-(2-ethoxy carbonyl allyloxy) ethylphosphonic acid.
Phosphonic acids with phosphonic acids hydrogen monoesters base is a monomer:
2-methylacryoyloxyethyl phosphonic acids list (methylacryoyloxyethyl) ester
2-methylacryoyloxyethyl phosphonic acids list phenylester.
In the present invention, total valence mumber of a solemnity (1) is than (R
E) be set in the predetermined scope, be the just not restriction of consumption of monomer (A1) to phosphoric acid, the total amount that for example can be monomer component (A) is that phosphoric acid is monomer (A1), in addition, can also be that the part of monomer component (A) is monomer (A1) for phosphoric acid.Yet, the permeability of the appropriateness that dentine is shown from adhesive composition, in addition from the viewpoint of the intensity that improves firming body, preferred and be that monomer (A1) is as monomer component (A) with the polymerizable monomer (A2) and the phosphoric acid that do not contain acidic-group.Especially, from the two all has good adhesive strength to enamel and dentin, preferably; Total amount in monomer component (A) is a benchmark; Use more than the 5 quality %, more preferably 5～80 quality %, most preferably the phosphoric acid of 10～60 quality % scopes is monomer (A1).Phosphoric acid be monomer (A1) use level more after a little while, adamantine bonding strength is had the trend of reduction, on the contrary phosphoric acid be monomer (A1) use level more for a long time, Dentinal bonding strength is had the trend of reduction.
As with phosphoric acid be monomer (A1) and usefulness do not contain acidic groups polymerizable monomer (below be called non-acidic monomers); Use has at least one above-mentioned polymerism unsaturated group and does not contain the chemical compound of acidic-group in molecule; Instantiation as this non-acidic monomers (A2); Can enumerate following chemical compound, these chemical compounds can use a kind of separately, perhaps can two or more combinations be used.
1. single (methyl) acrylic ester monomer:
(methyl) acrylic acid methyl ester.
(methyl) ethyl acrylate
(methyl) glycidyl acrylate
(methyl) acrylic acid 2-cyano methyl ester
(methyl) benzyl acrylate
Single (methyl) polyalkylene glycol acrylate ester
(methyl) allyl acrylate
(methyl) acrylic acid 2-hydroxyl ethyl ester
(methyl) glycidyl acrylate
(methyl) acrylic acid 3-hydroxypropyl acrylate
Single (methyl) acrylic acid glyceride
Acetoacetic acid 2-(methyl) acryloxy ethyl ester
2. polyfunctional group (methyl) acrylic ester monomer:
Two (methyl) acrylic acid glycol ester
Two (methyl) acrylic acid diethylene glycol ester
Two (methyl) acrylic acid triethyleneglycol ester
Two (methyl) acrylic acid, nine glycol esters
Two (methyl) acrylic acid propylene glycol ester
Two (methyl) acrylic acid dipropylene glycol ester
2,2 '-two [4-(methyl) acryloxy ethoxyl phenenyl] propane
2,2 '-two [4-(methyl) acryloxy ethoxy ethoxy phenyl] propane
2,2 '-two { 4-[3-(methyl) acryloxy-2-hydroxyl propoxyl group] phenyl } propane
Two (methyl) acrylic acid 1, the 4-butanediol ester
Two (methyl) acrylic acid 1,6-hexanediol ester
Trimethylolpropane tris (methyl) acrylic ester
(methyl) acrylic acid urethane ester
Epoxy radicals (methyl) acrylic ester
In addition, as non-acidic monomers (A2), can also be with at least a polymerizable monomer except above-mentioned (methyl) acrylic ester monomer and (methyl) acrylic ester monomer and usefulness.As these other non-acidic monomers (A2), can enumerate fumarate chemical compounds such as dimethyl fumarate, DEF, fumaric acid diphenyl ester; Polystyrene derivants such as styrene, DVB Diethenylbenzene, AMS, AMS dimer; Allyl compounds such as diallyl phthalate, diallyl p phthalate, carbonic acid diallyl, allyl diglycol carbonate; Deng.
In addition; When using the high polymerizable monomer of hydrophobicity as non-acidic monomers (A2); And, obtaining high bonding strength with amphiphilic medium property monomers such as (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylates, prevent the separation of sealing and guarantee that the composition aspect is preferred uniformly.
Adhesive composition for dental use of the present invention is owing to explain that as above containing phosphoric acid is monomer; Therefore present acidity usually, thereby shown de-ashing through this acid ingredient, yet; When discharging a large amount of metal ions from following polyvalent metal ion release property composition (B); Might in and acidic-group, can not present acidity, the reduction of de-ashing reduction and bonding strength and adhesion durability.In this case, can regulate acidity through the acidic materials that are used to regulate pH.Will be described below about this acidic materials that are used to regulate pH.
< polyvalent metal ion release property composition (B) >
As stated; In the present invention, the phosphoric acid that is comprised in the above-mentioned monomer component (A) is that monomer (A1) is very important with the earth metal ion coexist, is the monomer coexistence through making said earth metal ion and phosphoric acid; Fully carry out ionomer, thus the very high bonding strength of performance.In the present invention, as this earth metal ion supply source, use polyvalent metal ion release property composition (B).That is to say that this polyvalent metal ion release property composition (B) must can discharge the earth metal ion at least.
Above-mentioned earth metal is the metal that belongs to periodic chart IIIB family and group III A as previously mentioned, specifically, can enumerate rare earth metals such as yttrium, scandium and lanthanide ion; Aluminium family metals such as aluminum, gallium, indium.In addition, group of the lanthanides has lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutecium.In dental composition of the present invention, at least a ion of above-mentioned earth metal is emitted from polyvalent metal ion release property composition (B), with above-mentioned phosphoric acid be monomer (A1) coexistence.In above-mentioned earth metal ion, what effect was higher is aluminium ion and lanthanide ion, and in the middle of these, aluminium ion and lanthanum ion are preferred, most preferably lanthanum ion.For example, when multiple earth metal ion and phosphoric acid were monomer (A1) coexistence, their part was preferably lanthanum ion, it would be desirable, and be lanthanum ion more than the 10mol% in the earth metal ion.
In the present invention, from polyvalent metal release property composition (B) discharge and with phosphoric acid be that the ionic amount of earth metal of monomer (A1) coexistence is that monomeric total valence mumber is than (R with respect to phosphoric acid
E) be necessary for 0.2～3.0, especially be 0.3～0.9, optimum is 0.4～0.7 scope.This be because, at total valence mumber than (R
E) outside above-mentioned scope the time; Owing between the acidic-group that phosphoric acid is monomer (A1) to be had sufficient ionomer does not take place; In addition because de-ashing (to the etching of dentine) reductions etc. have damaged significant high bonding strength and resistance to water (or adhesion durability) as purpose.
In addition, as long as the earth metal ion of above-mentioned amount and phosphoric acid are monomer (A1) coexistence, other metal ion except above-mentioned earth metal ion can discharge and coexistence from polyvalent metal release property composition (B).As this other metal ion, can enumerate monovalence and bivalent metal ions such as alkali metal ion, alkaline-earth metal ions, can and deposit ferrum (III), ruthenium (III), cobalt trivalent metal ions such as (III) except above-mentioned earth metal ion in addition.Yet; Total ion valence mumber of these other metal ions that contained in the compositions is suitably for below 0.5 with respect to the ratio of total valence mumber (sum total of total valence mumber of the ionic total valence mumber of earth metal and other metal ion) of the whole metal ions that contain in the compositions, especially is below 0.2.That is to say, the metal ion except the earth metal ion with respect to total valence mumber of whole metal ions than (R
T) represent with following formula:
R
T＝TV
M/TV
T...(2)
In the formula, TV
MBe total valence mumber of the metal ion except the earth metal ion that contains in the said composition,
TV
TIt is total valence mumber of whole metal ions of containing in the said composition.
This total valence mumber is than (R
T) be suitably below 0.5, especially be suitably the scope below 0.2.This is because when other metal ion coexists in a large number, because other metal ion and phosphoric acid are the neutralization reaction of monomeric acidic-group, damaged the carrying out of the ionomer that is produced by the earth metal ion.
In addition, total valence mumber (TV of the whole metal ions in the formula (2)
T) calculate through following formula (2a):
TV
T＝∑I
k×B
k...(2a)
In the formula, k is 1,2,3..., n, and n is the number of the kind of each metal ion of containing in the compositions,
I
kBe the molal quantity of each metal ion of containing in the said composition,
B
kIt is the valence mumber of each metal ion.
The total valence mumber and the ionic total valence mumber (TV of above-mentioned earth metal of other metal ion that contains in the compositions in addition, or whole metal ions
E) likewise calculate.
In addition; Under the situation of other metal ion of except the earth metal ion, coexisting; All metal ions are that monomeric total ion valence mumber ratio becomes 1 when above with respect to phosphoric acid, because the acidity of adhesive composition is impaired, de-ashing reduces, so the bonding strength reduction.The earth metal ion is that monomeric total valence mumber is than (R with respect to phosphoric acid
E) be more than 1 situation too.Therefore, in this case, need regulate the acidity of compositions through the acidic materials that pH is regulated in following being used to.
In adhesive composition of the present invention, as above-mentioned polyvalent metal ion release property composition (B), can use is being that monomer (A1) can discharge total valence mumber than (R when in water, mixing with phosphoric acid
E) reach the ionic material of earth metal of the amount of predetermined value, for example, earth metal simple substance, earth metal compound and contain the earth metal ion stripping property filler of earth metal.But because the dissolubility of earth metal simple substance in water be very low, earth metal ion and above-mentioned phosphoric acid are that total valence mumber of monomer (A1) is than (R
E) reaching preset range might be for a long time, therefore, in the present invention, earth metal compound and earth metal ion stripping property filler suit.
As above-mentioned earth metal compound, can use the pKa value to be higher than slaine at least, promptly than the slaine of the acid a little less than the phosphoric acid based on the acid of the pKa value of the first stage ionization of phosphoric acid.This is that free earth metal ion and phosphoric acid are fully ionic bonding of monomeric acidic-group because when using the salt of the acid stronger than phosphoric acid.
As earth metal salt than the acid a little less than the phosphoric acid; Can enumerate carbonate, 1, the enolate of 3-diketone, citrate, tartrate, fluoride, malonate, glycollate, lactate, phthalate, M-phthalic acid salt, terephthalate, acetate, Methoxy acetic acid salt etc.In addition, be described below, in these faintly acid earth metal salt, the water solublity of some material is very low, therefore, can be in advance confirms its dissolubility and in that whether confirm can be to satisfy predetermined total valence mumber than (R with pilot study etc.
E) the amount release of ionic after re-use.In addition, as earth metal compound, can also use hydroxide, hydride or alkoxide.
According to the present invention; In above-mentioned earth metal compound; Because the ionic stripping of earth metal is rapid, by-product is gas or water, lower alcohol etc. at normal temperatures, is easy to remove by-product in last times such as compositions being applied to the dentine surface; Bonding strength there is not harmful effect, so hydroxide, hydride, carbonate or the carbon number rudimentary alkoxide below 4 is preferred.In addition, be easy to viewpoint from handling, hydroxide, alkoxide and carbonate are preferred.
In the present invention; As the instantiation of the earth metal compound that is especially suitable for use as polyvalent metal ion release property composition (B), can enumerate aluminium methoxide, aluminum isopropylate., aluminium hydroxide, aluminium acetylacetonate, ethanol gallium, ethanol indium, isopropyl alcohol scandium, yttrium isopropoxide, methanol lanthanum, ethanol lanthanum, lanthanum isopropoxide, lanthanum hydroxide, lanthanum carbonate, isopropyl alcohol cerium, isopropyl alcohol praseodymium, isopropyl alcohol promethium, isopropyl alcohol neodymium, isopropyl alcohol samarium, acetylacetone,2,4-pentanedione europium, acetylacetone,2,4-pentanedione gadolinium, acetylacetone,2,4-pentanedione terbium, acetylacetone,2,4-pentanedione dysprosium, acetylacetone,2,4-pentanedione holmium, acetylacetone,2,4-pentanedione erbium, acetylacetone,2,4-pentanedione thulium, isopropyl alcohol ytterbium, acetylacetone,2,4-pentanedione ytterbium, acetylacetone,2,4-pentanedione lutecium etc.Wherein, aluminium methoxide, aluminum isopropylate., aluminium hydroxide, methanol lanthanum, ethanol lanthanum, lanthanum isopropoxide, lanthanum hydroxide, lanthanum carbonate etc. are preferred especially.
In addition; The oxide of aluminum and lanthanum and carboxylate are insoluble material in polymerizable monomer or organic solvent mostly; Usually, even in the presence of water, the ionic stripping of this earth metal of above-mentioned necessary amount needs for a long time; Therefore, being not suitable for as the earth metal ion source is polyvalent metal ion release property composition (B).Especially, even therefore the oxide of aluminum and lanthanum also ion of stripping corresponding metal hardly in the presence of water, is difficult to use as polyvalent metal ion release property composition (B) usually.
In addition; The earth metal ion stripping property filler that comprises earth metal is can the said earth metal ion of stripping in presenting tart adhesive composition for dental use, and basically not stripping pKa value at the ionic filler of conjugate base based on the strong acid below the pKa value of the first stage ionization of phosphoric acid.Usually, as this filler, preferred use belong to have chain, the category of glass (for example oxide glass, fluoride glass etc.) of stratiform, cancellated skeleton and in the gap of its skeleton, keep the ionic filler of earth metal at least.For example, containing ionic glass of earth metal such as fluoride glasses such as oxide glasses such as alumina silicate glass, pyrex, Zirconium tetrafluoride. glass suits.In addition, can use and contain the ionic soda-lime glass of earth metal etc.
In addition; In the earth metal ion stripping property filler that constitutes by these category of glass; Residue composition after the stripping of earth metal ion generally is a porous particles, and former state when residual, can improve the intensity of firming body as supporting material in compositions; But this residue composition is owing to assemble or former thereby sedimentation in compositions such as particle diameter is big, and can remove through means such as filtrations as required this moment.
According to the present invention; In above-mentioned earth metal ion stripping property filler; Alumina silicate glass is particularly suitable, the optimal filler that is made up of aluminum fluoride glass fluoride ion, that have so-called fluorine slow-releasing that slowly discharges the reinforcement dentine in bonding back that is to use.
As the above-mentioned aluminum fluoride glass that can suit to use, can adopt as for example dental binding agent, for example the known material of glass ionomer cement use.In aluminum fluoride glass, contain a large amount of aluminum as above-mentioned earth metal, in addition,, also contain other earth metals such as lanthanum according to occasion.The composition of normally used aluminum fluoride glass is as follows.
The composition of aluminum fluoride glass:
Silicon: 5～33 quality %
Aluminum: 10～30 quality %
Lanthanum: 7～30 quality %
Calcium: 1～17 quality %
Sodium: 0～2 quality %
Phosphorus: 0.2～16 quality %
Fluorine: 2～40 quality %
Oxygen: surplus.
In the present invention, the composition of the aluminum fluoride glass of optimum use is as follows:
Silicon: 5～33 quality %
Aluminum: 10～30 quality %
Lanthanum: 10～30 quality %
Calcium: 1～3 quality %
Sodium: 0～1 quality %
Phosphorus: 0.5～5 quality %
Fluorine: 5～20 quality %
Oxygen: surplus.
In addition, also can use the aluminum fluoride glass of replacing the part of above-mentioned aluminum with other earth metals such as scandium, yttrium, ytterbiums.
In addition; When stating aluminum fluoride glass in the use, in this aluminum fluoride glass, contain the fluoride ion of a great deal of as the earth metal ion stripping property filler of composition (B), this fluoride ion stripping and with system in the water reaction; Generate fluohydric acid gas; But fluorion is not the conjugate base ion that has based on the strong acid of the pKa value below the pKa value of the first stage ionization of phosphoric acid, but than the conjugate base ion of the acid a little less than the phosphoric acid, though therefore in compositions, contain also no problem; According to its stripping quantity, regulate the acidity that the acidic materials of pH can be regulated adhesive composition through following being used to.
In the present invention; Grain shape to polyvalent metal ion release property compositions (B) such as earth metal ion stripping property fillers does not have specific limited; It can be the pulverizing shape granule that pulverize to obtain through routine, and perhaps spherical particle can be particulate mixture such as tabular, fibrous as required.
< water (C) >
In the present invention, in order from above-mentioned polyvalent metal ion release property composition (B), to discharge the earth metal ion of scheduled volume, be essential as the water of composition (C).This is because if there is not water, even cooperate a large amount of mentioned component (B), the earth metal ion can not emitted yet.
In the present invention, when adhesive composition of the present invention is coated the flank of tooth, consider that from the viewpoint that fully is cured it is preferred before said composition is solidified, removing above-mentioned water through blowing.In addition, also can after stripping earth metal ion, from compositions, remove through methods such as distilling under reduced pressure.
Because in the internal environment of oral cavity of using adhesive composition for dental use of the present invention, there is moisture to a certain degree; Therefore even in adhesive composition of the present invention under the water-free situation; Also can carry out the deliming of dentine through the predetermined de-ashing of adhesive composition for dental use, bring into play good bonding force.Yet,, preferably contain water in order to carry out dentine deliming more fully.
In the present invention, per 100 mass parts polymerizable monomer compositions (A) use this water (C) 3～150 mass parts, use 5～100 mass parts especially.
< aerosil (D) >
In adhesive composition for dental use of the present invention, except mentioned component (A)～(C), cooperating aerosil also is suitable as (D) composition.That is,, can significantly improve intensity and resistance to water that this adhesive composition solidifies the firming body that is obtained through adding aerosil.Therefore, when jointing material when using this adhesive composition or pretreating agent, the patience in the tensile stress of the interface of prosthesis and dentine generation is significantly improved as agglutinating repair thing and dentine.In addition, prosthesis is adhesively fixed the back to because the patience of the power that dental articulation produces also further improves on the reparation position of tooth, and prosthesis can keep steadily in the long term.
Like this, though to significantly improve the reason of firming body intensity not clear and definite, the inventor infers and is described below through cooperating aerosil (D).
Promptly; Think when in the presence of water, cooperating aerosil; The polymer of ionomer invades in the gap of flocculated particle of aerosil; Twine with aerosil, and, be present in the polyvalent metal ion that exists in silanol group and the compositions on the aerosil particle surface and combine through water.Therefore, can infer that in firming body, form the firm network of highdensity aerosil, the result causes bonding strength significantly to increase and water-proof further raising, thereby in long-time, has shown excellent durability.
Wherein, aerosil is meant the amorphous silicon di-oxide through the flame hydrolysis manufactured, specifically, and through Silicon chloride. pyrohydrolysis in hydrogen flame is prepared.The aerosil of making in this way is the average primary particle diameter (D with the volume conversion that measures by the laser diffraction and scattering method
50) be the subparticle about 5～100nm, have three grades of loose aggregated structures.That is to say that the firming body of ionomer twines the aggregated structure of this subparticle complicatedly, thereby forms firm high density network through water, shows very high bonding strength.For example; Aerosil silicon dioxide and the silicon dioxide inorganic filler in addition in addition that obtains with other manufacturing approach such as damp process, sol-gel process, Verneuil method is difficult to form three grades of loose aggregated structures in adhesive composition; Therefore; Do not form above-mentioned network, significantly the increasing of the bonding strength in the time of can not showing picture and use above-mentioned aerosil.
In the present invention, above-mentioned aerosil is not had specific limited, can use the BET specific surface area to be 70m usually
2More than/the g, especially be 100～300m
2The aerosil of/g scope.In addition, from through become key to form the viewpoint of the ability of network with said polyvalent metal ion, it is suitable having the aerosil of the silanol group of Sq from the teeth outwards.For example, there is 0.1/nm from the teeth outwards in preferred use
2More than, 0.5～2/nm especially
2The aerosil of silanol group of ratio.The lip-deep silanol group of aerosil number can be measured through Ka Er-Fei Xiu (Carl-Fischer) method through dry under 150 ℃ after this aerosil being flooded once in water.
In addition, the silanol group number on aerosil surface can be through being that the surface conditioning agent of representative carries out surface treatment and regulates in order to silane coupler.As this silane coupler; Can use MTMS, MTES, methyl trichlorosilane, dimethyldichlorosilane, trim,ethylchlorosilane, HMDS, vinyltrimethoxy silane, VTES, vinyl trichlorosilane, vinyltriacetoxy silane, vinyl three ('beta '-methoxy ethyoxyl) silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, gamma-methyl allyl acyloxypropyl three ('beta '-methoxy ethyoxyl) silane, γ-r-chloropropyl trimethoxyl silane, gamma-chloropropylmethyldimethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl methyldiethoxysilane, β-(3,4-ethyoxyl cyclohexyl) ethyl trimethoxy silane, N-phenyl-gamma-amino propyl trimethoxy silicane, HMDS etc. aptly.Especially preferably use methyl trichlorosilane, dimethyldichlorosilane, HMDS.
Use level to aerosil does not have specific limited; But from improving bonding strength; Tackify with compositions suppresses within the specific limits and keeps the infiltrative viewpoint to dentine simultaneously; Per 100 mass parts monomer components (A), aerosil is preferably 0.5～20 mass parts, is preferably 5～10 mass parts especially.
< polymerization initiator (E) >
The polymerization initiator (E) that in adhesive composition of the present invention, can cooperate effective dose especially when using as the dental jointing material, needs to cooperate polymerization initiator.
As this polymerization initiator (E), from can be in office when the viewpoint of machine polymerizing curable consider that Photoepolymerizationinitiater initiater is preferred.As Photoepolymerizationinitiater initiater, use the chemical compound that himself passes through rayed and produce free radical, or in this chemical compound, add the mixture etc. of polymerization accelerant.
Decompose and produce the chemical compound of polymerisable free radical along with rayed as himself, can enumerate following chemical compound:
α-two ketone:
Camphorquinone, benzil, α-naphthalene, acetonaphthone, naphthoquinone, 1,4-phenanthrenequione, 3,4-phenanthrenequione, 9,10-phenanthrenequione etc.
The thioxanthene ketone:
2,4-diethyl thioxanthone etc.
Norleucyl benzene class:
2-benzyl-dimethylamino-1-(4-morpholino phenyl)-1-butanone,
2-benzyl-diethylamino-1-(4-morpholino phenyl)-1-butanone,
2-benzyl-dimethylamino-1-(4-morpholino phenyl)-1-acetone,
2-benzyl-diethylamino-1-(4-morpholino phenyl)-1-acetone,
2-benzyl-dimethylamino-1-(4-morpholino phenyl)-1-pentanone,
2-benzyl-diethylamino-1-(4-morpholino phenyl)-1-pentanone etc.
The acylphosphine oxide derivant:
2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide etc.
In addition, as above-mentioned polymerization accelerant, can use tertiary amine, barbital acids, sulfhydryl compound etc.Their instantiation is described below.
Tertiary amines:
N, accelerine,
N, the N-diethylaniline,
N, N-di-n-butyl aniline,
N, the N-dibenzyl aniline,
N, N-dimethyl-para-totuidine,
N, N-diethyl-para-totuidine,
N, N-dimethyl-meta-aminotoluene,
Right-bromo-N, accelerine,
Between-chloro-N, accelerine,
Right-the dimethylamino benzaldehyde,
Right-dimethylamino acetyl benzene,
Right-dimethylaminobenzoic acid,
Right-the dimethylaminobenzoic acid ethyl ester,
Right-the dimethylaminobenzoic acid pentyl ester,
N, N-dimethyl methyl 2-aminobenzoate,
N, N-dihydroxy ethyl aniline,
N, N-dihydroxy ethyl-para-totuidine,
Right-the dimethylamino phenethanol,
Right-dimethylaminostilbene,
N, N-dimethyl-3, the 5-dimethylaniline,
4-dimethylaminopyridine,
N, the N-dimethyl-,
N, N-dimethyl-beta-naphthylamine,
Tri-n-butylamine,
Tripropyl amine (TPA),
Triethylamine,
N methyldiethanol amine,
The N-ethyldiethanolamine,
N, the N-dimethylhexylamine,
N, N-dimethyl lauryl amine,
N, N-dimethyl stearylamine,
Acrylic acid N, N-dimethyl aminoethyl ester,
Methacrylic acid N, N-dimethyl aminoethyl ester,
2,2 '-(normal-butyl imino group) diethanol etc.
The barbital acids:
The acid of 5-soneryl,
1-benzyl-5-phenyl barbiturates etc.
Sulfhydryl compound:
Lauryl mercaptan,
Tetramethylolmethane four (mercaptoacetate) etc.
Use level to this polymerization initiator (E) does not have specific limited, can suit to set, so long as can solidify the effective dose of this adhesive composition.Usually, the monomer component of per 100 mass parts (A), the use level of this polymerization initiator (E) is 0.01～10 mass parts, especially 0.1～5 mass parts.When being lower than 0.01 mass parts, it is insufficient that polymerization becomes easily, and when surpassing 10 mass parts, the intensity of firming body often reduces.
<being used to regulate the acidic materials of pH >
As stated; Adhesive composition for dental use of the present invention is that monomer (A1) is as monomer component (A) owing to containing the phosphoric acid with acidic-group; Thereby presenting acidity usually, the existence through this acid ingredient has shown de-ashing, and dentine is had high osmosis.That is, it is the one of the main reasons that said composition shows high bonding strength that adhesive composition for dental use of the present invention presents acidity, in addition, can need not the etch processes of dentine and uses as jointing material, and in addition, said composition can also be used as pretreating agent.Therefore, in order to maximally utilise above-mentioned advantage, compositions of the present invention preferably has high acidity.For example, its pH is below 4.8, especially 0.5～4.0, and preferred especially 1.0～3.0 scope.
In addition; The pH of this adhesive composition mixes with the concentration of 10 quality % this adhesive composition with ethanol, through using the values of under 25 ℃, measuring with the pH meter of neutral phosphor hydrochlorate pH titer (pH6.86) and the gauged pH electrode of phthalate pH titer (pH4.01).The alcoholic acid purity that is used to dilute is more than 99.5%, and the independent pH value of this ethanol can be 4.8～5.0.
The earth metal ionic weight that above-mentioned polyvalent metal ion release property composition (B) is emitted is big and be that total valence mumber of monomer (A1) is than (R with respect to phosphoric acid
E) be 1 when above, because phosphoric acid is monomeric acidic-group and earth metal ions bind, can not present acidity, deliming property is compromised, and causes unfavorable condition generations such as bonding strength reduction.Total valence mumber that many, the whole metal ions of this amount with whole metal ions of from composition, emitting are monomer (A1) with respect to phosphoric acid is than being that situation more than 1 is identical.Therefore in this case, need to cooperate the acidic materials except phosphoric acid is monomer (A1) to regulate pH, for example, with the adjusting pH of compositions in above-mentioned scope.
In the present invention,, use the pKa value in 25 ℃ water to surpass 2.15 material as the above-mentioned acidic materials that are used to regulate pH, that is, acid than the material a little less than the phosphoric acid.As stated, this is because when using than the strong acidic materials of phosphoric acid, earth metal ion and phosphoric acid are that monomeric acidic-group can not form ionomer.In addition, from the viewpoint strong to the deliming function of dentine, the pKa value of this acidic materials is suitably below 6.0, especially below 4.0.As this suitable instance that is used to regulate the acidic materials of pH, can enumerate citric acid, tartaric acid, Fluohydric acid., malonic acid, glycolic, lactic acid, phthalic acid, M-phthalic acid, p-phthalic acid, Methoxy acetic acid etc.
In addition, as the acidic materials that are used to regulate pH, can also the part of above-mentioned non-acidic monomers (A2) be replaced with and have except using by the acidic-group the deutero-acidic-group of phosphoric acid and after having the polymerizable monomer of above-mentioned pKa value.As this polymerizable monomer that can be used for regulating pH, can enumerate 2-(6-methacryloxypropyl hexyl) malonic acid, 2-(10-methacryloxypropyl decyl) malonic acid, trimellitic acid-4-(2-methylacryoyloxyethyl) ester, N-methacryl glutamic acid, 1,2; 4,5-benzene tetracarboxylic acid-2, two (2-methylacryoyloxyethyl) esters, 3 of 4-; 3; 4,4-xenyl tetracarboxylic acid-4, two (2-methylacryoyloxyethyl) esters of 4-etc.
In addition, in order to regulate pH, when using above-mentioned phosphoric acid to be in addition acidic materials of monomer (A1), if these acidic materials surpass aequum when using in a large number, earth metal ion and phosphoric acid are that the acidic-group of monomer (A1) might be difficult to form ionomer.Therefore, when using this acidic materials to regulate pH, each part be acidic materials (phosphoric acid is monomer+other acidic materials) all, and phosphoric acid is that monomer (A1) is preferably more than the 20mol%, more preferably more than the 40mol%.
< other compounding ingredient >
In the scope that does not reduce characteristic, dental adhesive composition of the present invention can contain known various compounding ingredients in the dental field beyond the mentioned component.
For example, except above-mentioned polymerization initiator (E), electron acceptors such as iodine salt, the substituted s-triazine of trihalomethyl group, phenacyl sulfosalt chemical compound can be cooperated,, polymerization activity can be improved through cooperating this electron acceptor.
In addition, as the dental jointing material time, can use above-mentioned aerosil (D) inorganic filler in addition, for example the silicon dioxide beyond the aerosil, zirconium oxide, titanium dioxide, silicon dioxide-zirconium oxide, silica-titania etc.Use this inorganic filler in order to improve mechanical strength and resistance to water, can also be through carrying out surface treatment with above-mentioned silane coupler and re-using behind the hydrophobization.Through this hydrophobization,, thereby can seek further to improve mechanical strength and resistance to water with the affinity raising of monomer component (A).
Usually, the use level of this inorganic filler beyond the monomer component of per 100 mass parts (A), aerosil is 2～400 mass parts, especially 5～100 mass parts.Especially, when using adhesive composition to use jointing material as composite resin, in compositions, can cooperate 2～20 mass parts, especially be 5～10 mass parts.
In addition, for the viscosity of regulating adhesive composition or with monomer component (A) homodisperse in compositions, can also cooperate the volatile, water-soluble organic solvent.That is, the boiling point of this organic solvent under 760mmHg is below 100 ℃, and under 20 ℃, has the vapour pressure more than the 1.0KPa, and the dissolubility under these external 20 ℃ in water is more than the 20g/100ml.As this volatile water-miscible organic solvent, can enumerate methanol, ethanol, normal propyl alcohol, isopropyl alcohol, acetone, butanone etc.As required, can these multiple organic solvents be mixed use.Consider the toxicity to organism, ethanol, isopropyl alcohol and acetone are preferred.
The use level of these volatile organic solvents according to the kind of employed monomer component (A) with amount and different.Usually, the monomer component of per 100 mass parts (A), the use level of this volatile organic solvent is suitably 2～400 mass parts, especially is 5～100 mass parts.
In addition, the same with above-mentioned water, when coating adhesive composition of the present invention on the flank of tooth,, these volatile organic solvents are removed this adhesive composition before solidifying through blowing.
In addition, except above-mentioned compounding ingredient, as required, can add organic tackify materials such as macromolecular compound such as polyvinylpyrrolidone, carboxymethyl cellulose, polyvinyl alcohol.In addition, can cooperate various additives such as UV absorbent, dyestuff, antistatic additive, pigment, spice as required.
< preparation of dental composition and use >
Adhesive composition for dental use of the present invention can pass through above-mentioned various composition uniform mixing, the earth metal ion concentration is adjusted in the preset range to prepare then.
The acidic materials such as acidic materials that it is monomer (A1) that though said composition contains phosphoric acid, be used to regulate pH; But as stated; Do not use acidity to be better than the acidic materials of phosphoric acid; Specifically, do not use the strong acid that has based on the pKa value below the pKa value (2.15) of the first stage ionization of phosphoric acid in 25 ℃ of water.That is to say that if the conjugate base ion packet of this strong acid is contained in the adhesive composition, then the bonding strength of firming body reduces.This be because, the conjugate base ion of said strong acid and above-mentioned earth metal ion are competed, with phosphoric acid be that the acidic-group that monomer (A1) is had carries out ionic bonding, the result suppresses to form ionomer between earth metal ion and this acidic-group.
In addition, as the strong acid with above-mentioned pKa value, representative example has mineral acids such as hydrochloric acid, bromic acid, iodic acid, sulphuric acid, nitric acid; Organic acid such as alkylsurfuric acid and sulfonic acid.As the ionic representative example of the conjugate base corresponding, can enumerate inorganic acid ions such as chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion with these strong acid; Organic acid ion such as alkyl sulfate ion and sulfonate ion.
Therefore; The content of conjugate base ion in adhesive composition for dental use of the present invention to above-mentioned strong acid has restriction, and for example, its content should be limited in respect to below the ionic 5mol% of earth metal; Especially the scope below the 3mol% most preferably is substantially devoid of.
In the present invention, the conjugate base ion that whether contains this strong acid in the compositions can be confirmed with ion-chromatographic determination.Specifically, water extraction adhesive composition filters the gained water, should filtrate with ion-chromatographic determination, thereby can confirm.
Multivalent ion release property composition (B) is so that the earth metal ionic weight of being emitted is that total valence mumber of monomer (A1) is than (R with respect to phosphoric acid
E) amount of (0.2～3.0) is used in above-mentioned scope, yet when just various compositions being mixed, total valence mumber is than (R
E) not in above-mentioned scope, need carry out the ripening of certain hour.That is, this is because need certain hour from multivalent ion release property composition (B) with the earth metal ion to the release scheduled volume after other composition that contains water mixes.Especially; In the present invention; Consider from the viewpoint of the intensity that helps to improve the residue composition; As multivalent ion release property composition (B), suitable use contains the earth metal ion stripping property filler of earth metal, but this earth metal ion stripping property filler needs more than 10 hours till discharging a certain amount of earth metal ion.Therefore,, need carry out ripening according to the kind and the amount of employed multivalent ion release property composition (B), until total valence mumber than (R
E) reach predetermined value.
The compositions that above-mentioned ripening can prepare whole compositions mixing is usually at room temperature placed just passable, and for example, when using aluminum fluoride glass as composition (B), the curing time at ambient temperature was at least 12 hours.In addition, use curing time under the situation such as salt of earth metal can be several minutes with the interior short time.In addition, also can with compositions heat to suitable temperature (for example about 30～40 ℃) to shorten the curing time.
Through above-mentioned ripening, jointing material that adhesive composition for dental use of the present invention can use when dental restorations such as composite resin, prosthesis are bonded in dentine and the jointing material that uses when carriage Dentition correctings such as (Bracket) is bonded in the flank of tooth with utensil.In addition, owing to have deliming function,, use with material previously treated as dentine so can also mismatch polymerization initiator (E) etc. to dentine.
In addition, tooth of the present invention section with adhesive composition at the ionic total valence mumber of earth metal than (R
E) reach predetermined value afterwards through after long-time, might produce gelation.Therefore, it is desirable to, at the ionic total valence mumber of earth metal than (R
E) reach after the predetermined value, before producing this gelation, use as for example jointing material or pretreating agent as early as possible.
< embodiment >
Below come to explain particularly the present invention through experimental example, yet the present invention does not receive the restriction of these experimental examples.
In addition, experimental example (I) is in order to explain that in adhesive composition of the present invention be that total valence mumber of monomer (A1) is than (R with the earth metal ion with respect to phosphoric acid
E) having obtained the example of required bonding strength when being set in the preset range, experimental example (II) is to be illustrated in the example that bonding strength when cooperating aerosil in the adhesive composition of the present invention improves effect.
In each experimental example, abbreviation, shorthand notation, bonding strength assay method, storage stability evaluation methodology and polyvalent metal ion quantity measuring method are described below.
Polymerizable monomer composition (A)
[phosphoric acid is monomer (A1)]
PM1：
Biphosphate 2-methylacryoyloxyethyl ester
PM2：
Two (2-methylacryoyloxyethyl) esters of phosphoric acid hydrogen
2: 1 the mixture of PM:PM1 and PM2
MDP：
Biphosphate 10-methacryloxy decyl ester
HP：
[polymerizable monomer that contains other acidic-group]
MAC-10：
[polymerizable monomer (A2) that does not contain acidic-group]
BisGMA：
2,2 '-two [4-(2-hydroxy-3-methyl acryloxy propoxyl group) phenyl] propane
3G：
The dimethacrylate triethyleneglycol ester
HEMA：
Methacrylic acid 2-hydroxyl ethyl ester
Polyvalent metal ion release property composition (B)
Al (O-i-Pr)
3: aluminum isopropylate
Al (OH)
3: aluminium hydroxide
La (O-i-Pr)
3: three lanthanum isopropoxides
La (OH)
3: lanthanum hydroxide
Sc (O-i-Pr)
3: three isopropyl alcohol scandiums
Yb (O-i-Pr)
3: three isopropyl alcohol ytterbiums
Mg (OH)
2: magnesium hydroxide
Ca (OH)
2: calcium hydroxide
Ba (OH)
2: barium hydroxide
Ti (O-i-Pr)
4: titanium tetraisopropylate
Zr (O-i-Pr)
4: four zirconium iso-propoxides
V (acac)
3: four vanadium acetylacetonates (III)
Cr (O-i-Pr)
3: three isopropyl alcohol chromium (III)
Mn (acac)
3: four manganese acetylacetonates (III)
Fe (OEt)
3: ethanol ferrum (III)
Co (acac)
3: tetra-acetylated acetone cobalt (III)
Ni (acac)
2: tetra-acetylated acetone nickel (II)
Cu (OEt)
2: ethanol copper (II)
W (OEt)
6: ethanol tungsten (VI)
Zn (OCH
2CH
2OMe)
2: two (2-methyl cellosolve) zinc
Al
2O
3: alumina particle (mean diameter 13nm)
Al (sal)
3: salumin
AlCl
3: aluminum chloride
MF：
Use continuous ball mill (the ニ ユ one マ イ ミ Le of wet type; Mitsui mine manufactured) with aluminum fluoride glass powder (Tokuso Ionomer; TOKUYAMADENTAL CORPORATION manufacturing) being crushed to mean diameter is 0.5 μ m; Every 1g powder was handled 15 minutes filling surface with 20g5.0N hydrochloric acid, obtained earth metal ion stripping property filler.
Mean diameter: 0.5 μ m
24 hours released ion amounts: 27meq/g-filler
[volatile, water-soluble organic solvent]
IPA: isopropyl alcohol
[polymerization initiator]
CQ: camphorquinone
DMBE: right-N, N-dimethylaminobenzoic acid ethyl ester
TPO:2,4,6-trimethylbenzoyl diphenyl phosphine oxide
BTPO：
Two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxides
[polymerization inhibitor]
BHT:2,6-di-t-butyl-paracresol
[aerosil]
FS1: untreated aerosil
Average primary particle diameter 18nm
Specific surface area 220m
2/ g
The several 5/nm of silanol group
2
FS2: the aerosil that methyl trichlorosilane is handled
Average primary particle diameter 18nm
Specific surface area 120m
2/ g
The several 1.2/nm of silanol group
2
FS3: the aerosil that dimethyldichlorosilane and HMDS are handled
Average primary particle diameter 18nm
Specific surface area 200m
2/ g
The several 1/nm of silanol group
2
FS4: the aerosil that methyl trichlorosilane is handled
Average primary particle diameter 40nm
Specific surface area 50m
2/ g
Methyl trichlorosilane is handled
The several 1.3/nm of silanol group
2
FS5: the aerosil that dimethyldichlorosilane and silicone oil are handled
Average primary particle diameter 18nm
Specific surface area 200m
2/ g
The several 0.3/nm of silanol group
2
[other inorganic filler]
The fused silica that the MS:3-methyl allyl acyloxypropyl trimethoxysilane is handled
Average primary particle diameter 0.4 μ m
Specific surface area 8m
2/ g
The several 2/nm of silanol group
2
The sol-gel silicon dioxide that the SS:3-methyl allyl acyloxypropyl trimethoxysilane is handled
Average primary particle diameter 60nm
Specific surface area 70m
2/ g
The several 3/nm of silanol group
2
The sedimentation silicon dioxide that the PS:3-methyl allyl acyloxypropyl trimethoxysilane is handled
Average primary particle diameter 30nm
Specific surface area 180m
2/ g
Silanol group number＞5/nm
2
MF1: make the polyvalent metal filler that example 1 obtains
Mean diameter 0.5 μ m
24 hours released ion amounts: 10meq/g-filler
MF2: make the polyvalent metal filler that example 2 obtains
Mean diameter 0.5 μ m
24 hours released ion amounts: 25meq/g-filler
MF3: make the polyvalent metal filler that example 3 obtains
Mean diameter 0.5 μ m
24 hours released ion amounts: 50meq/g-filler
In addition, the various mensuration in each experimental example are carried out as follows.
(1) mensuration of metal ion:
Various compositions are mixed, and preparation adhesive composition test portion stirred 24 hours then, and weighing 0.2g compositions joins 100ml in vitro, uses IPA to be diluted to 1 quality %.With this liquid filtering, use ICP (inductive type plasma) emission spectrometry method analysis filtrating with the syringe-type filter, measure and contain each concentration of metal ions (mmol/g) in every 1g polymerizable monomer.
(2) phosphoric acid is monomeric mensuration
Be determined at the IPA solution that uses in the mensuration of above-mentioned amount of metal ion with HPLC, measuring the phosphoric acid that contains in every 1g polymerizable monomer is monomeric concentration (mmol/g).
In addition, according to above-mentioned formula (1) and formula (2), by the concentration of each metal ion of measuring as stated and phosphoric acid be monomeric concentration calculate each compositions the ionic total valence mumber of earth metal than (R
E) and all total valence mumber of metal ions than (R
T).
(3) anionic mensuration
2g adhesive composition test portion is fully mixed with 100g water and 10g diethyl ether, after leaving standstill, filter water,, record the anion concentration (mmol/g) that every 1g polymerizable monomer is contained through ion-chromatographic determination gained filtrating with the syringe-type filter.
(4) pH of adhesive composition measures
2g adhesive composition test portion is mixed with the 8g dehydrated alcohol, use with neutral phosphor hydrochlorate pH titer (pH6.86) and the gauged pH electrode of phthalate pH titer (pH4.01) (GTS-5211C, DKK-TOA CORPORATION) its pH of rapid test.
(5) adhesion durability test
(a) the manufacture method I of adhesive test sheet (being suitable for evaluation) as the dental jointing material
Pull up and butcher back 24 hours, under water filling, go out enamel and dentin face with the mode grinding that is parallel to labial surface (labial face), make strength test and use tooth with the emery paper of #600 with interior cattle front tooth.
Then; Send compressed air to carry out drying about 10 seconds to strength test with the above-mentioned top blast of tooth; The two-sided tape that will have the hole of diameter 3mm then is fixed on enamel and Dentinal any one; Be that the paraffin in the hole that has diameter 8mm of 0.5mm is fixed on the above-mentioned circular hole with thickness then, make paraffin and above-mentioned circular hole that same center arranged, form simulation nest hole.
Coat binding property compositions test portion in this simulation nest hole placed for 20 seconds, and compressed-air blows is carried out drying about 10 seconds then, shines for 10 seconds with dental radiation of visible light device (TOKUSO POWER LITE, TOKUYAMA manufactured).In addition, fill dental composite resin (ESTELITE ∑, TOKUYAMADENTAL CORPORATION make) above that, with 30 seconds of radiation of visible light device rayed, test film I is used in the evaluation of making jointing material.
(b) the manufacture method II of adhesive test sheet (being suitable for evaluation) as material previously treated
The strength test that forms as stated with tooth simulation nest hole in the test portion of coat binding property compositions; Place after 20 seconds compressed-air blows and carry out drying about 10 seconds; Be coated with two rank type composite resins above that with the jointing material (binding material of TOKUSO MACBONDII; The TOKUYAMA manufactured), shone for 10 seconds with dental radiation of visible light device (TOKUSO POWER LITE, TOKUYAMA manufactured).In addition, fill dental composite resin (ESTELITE ∑, TOKUYAMA DENTAL CORPORATION make) above that, with 30 seconds of radiation of visible light device rayed, test film II is used in the evaluation of making pretreating agent.
(c-1) adhesive test A
The jointing material evaluation is put into the thermal shock test device with test film I or pretreating agent evaluation with test film II; Dipping is 1 minute in 4 ℃ tank; Transfer in 60 ℃ the tank dipping then 1 minute, and returned once more in 4 ℃ the tank, repeat above operation 3000 times.
After this, use cupping machine (Autograph, Shimadzu Seisakusho Ltd. makes) to stretch, measure the tensile adhesion strength of enamel or dentin and composite resin with the crosshead speed of 2mm/min.Each test is measured 4 tensile adhesion strength with said method, and the bonding strength of its meansigma methods after as long duration test measured, and estimates adhesion durability.
(c-2) adhesive test B
In adhesive test A, the jointing material evaluation is put into the thermal shock test device with test film I or pretreating agent evaluation with test film II, in 4 ℃ tank, flooded 1 minute then; Transferred in 60 ℃ the tank dipping then 1 minute; Return once more in 4 ℃ the tank, the number of repetition of operation is increased to 6000 times, in addition; Likewise measure the bonding strength after the long duration test with adhesive test A, thereby estimate the adhesion durability under stricter environment.
< experimental example (I) >
(embodiment 1)
Use 1.5gPM (phosphoric acid is monomer), 3.0gBisGMA, 2.0g3G and 3.5gHEMA as polymerizable monomer composition (A), use the 0.4g aluminum isopropylate., in addition, use 0.1g camphorquinone and 0.15gDMBE as polymerization initiator (E) as earth metal ion source (B).These compositions and 8.5gIPA (organic solvent), 1.5g distilled water (C) and 0.03gBHT (polymerization inhibitor) were mixed 24 hours, prepare adhesive composition for dental use of the present invention (composite resin is used jointing material).
The pH that carries out this adhesive resin composition according to the method described above measures and is the relevant various mensuration of monomer, metal ion and anion with phosphoric acid.In addition, make the jointing material evaluation according to the method described above and use test film I, estimate enamel and Dentinal adhesion durability through adhesive test A.The composition of adhesive composition is shown in the table 1, and evaluation result is shown in the table 2.
(embodiment 2～20)
According to the method for embodiment 1, the adhesive composition (composite resin is used jointing material) of the composition of preparation shown in the table 1 carries out with the same mensuration of embodiment 1 with according to the adhesion durability evaluation of adhesive test A, and the result is shown in the table 2.
(embodiment 21)
Using 1.5gPM is monomer (A1) as phosphoric acid, uses the 1.0g aluminum fluoride glass as earth metal ion supply source (B), and these compositions and 8.5gIPA (organic solvent), 1.5g distilled water (C) and 0.03gBHT (polymerization inhibitor) were mixed 24 hours.
Then, distill water and IPA, in addition, used the vacuum pump drying under reduced pressure 2 hours with Rotary Evaporators.In the dry thing of gained, add 3.0gBisGMA, 2.0g3G and 3.5gHEMA as polymerizable monomer composition (A); 0.1g camphorquinone and 0.15gDMBE and 10.0gIPA (organic solvent) as polymerization initiator (E); Stir preparation adhesive composition (composite resin is used jointing material).
This adhesive composition is carried out with the same mensuration of embodiment 1 and according to the adhesion durability evaluation of adhesive test A, and it is formed shown in the table 1, and the evaluation result of adhesion durability is shown in the table 2.
(comparative example 1～26)
Prepare the adhesive composition of forming shown in the table 3 (composite resin is used jointing material) according to the method for embodiment 1, carry out with the same mensuration of embodiment 1 and according to the adhesion durability evaluation of adhesive test A, its evaluation result is shown in the table 4.
(comparative example 27)
Except the mixing mixing time of each composition was changed into 1 hour from 24 hours, identical with embodiment 12, preparation and the embodiment 12 same adhesive compositions of forming.This adhesive composition is carried out with the same mensuration of embodiment 1 and according to the adhesion durability evaluation of adhesive test A, and it is formed shown in the table 3, and the evaluation result of adhesion durability is shown in the table 4.
Table 1
Table 2
Table 3
Table 4
The formation of the compositions of embodiment 1～21 is that monomeric total valence mumber is than (R owing to satisfying the earth metal ion with respect to phosphoric acid
E) in the scope that the present invention is scheduled to, all be very high therefore to enamel and Dentinal adhesion durability.
To this, even therefore the compositions of comparative example 1～18 metal ion or contain metal ion and also do not contain the earth metal ion not fully, as the result of the test of durability, all is low to dentin and adamantine bonding strength.
In comparative example 19, owing to use aluminium oxide, have basically no Al ion (earth metal ion) stripping as earth metal ion source (B), particularly quite low to Dentinal bonding strength.
In comparative example 20, though use salumin as the earth metal ion source, the ionic stripping of Al is considerably less, and is therefore, particularly quite low to Dentinal bonding strength.
In comparative example 21, use aluminum chloride as the earth metal ion source, the stripping of Al ion, but, particularly dentin is not obtained good adhesive strength because the conjugate base ion that contains as the strong acid stronger than phosphoric acid is chloride ion (pKa of hydrochloric acid is-6.1).
In comparative example 22～25, though there is the earth metal ion, total valence mumber is than (R
E) outside scope of the present invention, perhaps compositions is not acid, therefore, all low to dentin and adamantine bonding strength.
In comparative example 26, contain the polymer that phosphoric acid is the acidic-group beyond the monomer owing to used, particularly enamel is not obtained good cohesive.
Though comparative example 27 uses aluminum fluoride glass as earth metal ion source (B); And the earth metal ionic weight that contains in this glass is adjusted in the scope of the present invention; But because mixing time (curing time) is as short as 1 hour, the ionic stripping of earth metal is considerably less.As a result, particularly low to Dentinal bonding strength.
(embodiment 22～29, comparative example 28～33)
Use each composition according to the composition described in table 5 or the table 7, likewise prepare adhesive composition (pretreating agent) with embodiment 1.Estimate the various mensuration of said composition and to enamel and Dentinal bonding strength.These results are shown in table 6 and the table 8.
Table 5
Annotate 1: the BHT that contains 0.03 mass parts
Table 6
Table 7
Table 8
Embodiment 22～29 all is good so that each composition satisfies the mode of formation shown in the present to be cooperated to enamel and Dentinal adhesion durability.
Even comparative example 28～33 does not perhaps contain the earth metal ion owing to do not contain the earth metal ion, Zong valence mumber is than (R
E) also be outside scope of the present invention, particularly can not obtain good adhesive strength to dentin.
< experimental example (II) >
< experiment 1 >
Except further interpolation 0.7gFS2 as the aerosil, likewise prepare adhesive composition for dental use (composite resin is used jointing material) with embodiment 1.
Likewise above-mentioned composition is carried out that pH measures with embodiment 1 and with phosphoric acid be the relevant various mensuration of monomer, metal ion and anion; In addition; Make the jointing material evaluation and use test film I, enamel and Dentinal adhesion durability are estimated according to adhesive test B.
The monomer of above-mentioned composition is formed shown in the table 9, and the cooperation of the composition beyond the polymerizable monomer is formed shown in the table 10, and phosphoric acid is that monomeric amount and the ionic amount of earth metal are shown in the table 11.In addition, to have provided the earth metal ion be that monomeric total valence mumber is than (R with respect to phosphoric acid to table 12
E), the result of the pH of compositions and adhesion durability test.
< experiment 2～24 >
Kind and use level to aerosil are carried out various changes; Definition simultaneously changes the cooperation of other composition and forms; Likewise prepare adhesive composition for dental use (composite resin is used jointing material) with experiment 1, carry out various mensuration and estimate adhesion durability according to adhesive test B.
The monomer of each compositions of gained is formed shown in the table 9; The cooperation of the composition beyond the polymerizable monomer is formed shown in the table 10; Phosphoric acid be monomeric amount and earth metal ionic weight shown in the table 11, it is that monomeric total valence mumber is than (R that earth metal ion pair phosphoric acid has been shown in the table 12
E), the result of the pH of compositions and adhesion durability test.
< control experiment 1～8 >
Except using other inorganic filler to replace aerosil and carrying out the various changes to cooperating to form; Likewise prepare adhesive composition for dental use (composite resin is used jointing material) with experiment 1, carry out various mensuration and estimate adhesion durability according to adhesive test B.
The monomer of each compositions of gained is formed shown in the table 13, and the cooperation of the composition beyond the polymerizable monomer is formed shown in the table 14, phosphoric acid be monomeric amount and earth metal ionic weight shown in the table 15, the earth metal ion is that monomeric total valence mumber is than (R with respect to phosphoric acid
E), the result of the pH of compositions and adhesion durability test is shown in the table 16.
Table 9
Annotate 1: the BHT that contains 0.03 mass parts
Table 10
Table 11
Table 12
Table 13
Annotate 1: the BHT that contains 0.03 mass parts
Table 14
Table 15
Table 16
Can draw from above-mentioned experimental result; Compare with cooperating other inorganic filler, when cooperating aerosil, adhesion durability improves greatly; In addition enamel and dentin all having been showed significant bonding raising effect, is very useful as composite resin with jointing material.
< experimental example 25～33, control experiment example 9～11 >
Except forming, likewise prepare the adhesive composition that uses as pretreating agent with experiment 1 according to the cooperation of table 17.
These compositionss are carried out that pH measures and are the relevant various mensuration of monomer, metal ion and anion with phosphoric acid, in addition, make the pretreating agent evaluation and use test film II, test enamel and Dentinal adhesion durability according to adhesive test B.
The result of the test of various mensuration results and adhesion durability is shown in the table 18.
Table 17
Annotate 1: the BHT that contains 0.03 mass parts
* 9～11 are the control experiment example
Table 18
* 9～11 are the control experiment example
Can find out in the adhesive composition of the present invention as the pretreating agent use,, enamel and Dentinal cohesive to be had significant raising effect through cooperating aerosil from above-mentioned experimental result.
Claims (10)
1. adhesive composition for dental use; Said compositions is to be that the polymerizable monomer composition (A) of polymerizable monomer mixes the tart adhesive composition for dental use that appears that obtains with polyvalent metal ion release property composition (B) through containing phosphoric acid; Wherein, Said phosphoric acid is that polymerizable monomer has by the deutero-acidic-group of phosphoric acid, it is characterized in that
Said polyvalent metal ion release property composition (B) can discharge the earth metal ion at least,
The earth metal ion and the phosphoric acid that come from said composition (B) are that polymerizable monomer is present in the said composition jointly, and with total valence mumber of following formula (1) definition than (R
E) in 0.2～3.0 scope:
R
E＝TV
E/TV
A...(1)
In the formula, TV
EBe the ionic total valence mumber of earth metal that contains in the said composition, TV
ABe that the phosphoric acid that contains in the said composition is total valence mumber of the acidic-group of polymerizable monomer,
Said is biphosphate monoesters group and/or phosphoric acid hydrogen two ester groups by the deutero-acidic-group of phosphoric acid,
Said polyvalent metal ion release property composition (B) is earth metal compound or earth metal ion stripping property filler,
Said earth metal compound is the hydroxide or the alkoxide of earth metal,
Said earth metal is meant rare earth metal or aluminium family metal.
2. adhesive composition for dental use according to claim 1, wherein said earth metal are aluminum and/or lanthanum.
3. adhesive composition for dental use according to claim 1, wherein said composition (B) are the rudimentary alkoxide of carbon number below 4 of earth metal.
4. it is polymerizable monomer that adhesive composition for dental use according to claim 1, wherein said polymerizable monomer composition contain the above phosphoric acid of 5 quality %.
5. adhesive composition for dental use according to claim 1, it further contains water (C).
6. adhesive composition for dental use according to claim 1, it further contains aerosil (D).
7. adhesive composition for dental use according to claim 1, it further contains polymerization initiator (E).
8. dental jointing material, it comprises the adhesive composition for dental use of claim 1.
9. a dentine is used pretreating agent, and it comprises the adhesive composition for dental use of claim 1.
10. the manufacturing approach of an adhesive composition for dental use is characterized in that,
With (A), (B) and (C) uniform mixing:
(A) contain the polymerizable monomer composition that phosphoric acid is polymerizable monomer, said phosphoric acid is that polymerizable monomer has by the deutero-acidic-group of phosphoric acid;
(B) can discharge the ionic polyvalent metal ion release property of earth metal composition at least; And
(C) water,
Then, with this mixture ripening, the total valence mumber that makes the ionic amount of earth metal that is discharged by said composition (B) in the gained mixture reach to define with following formula (1) is than (R
E) in 0.2～3.0 scope:
R
E＝TV
E/TV
A...(1)
In the formula, TV
EBe the ionic total valence mumber of earth metal that contains in the said composition, TV
ABe that the phosphoric acid that contains in the said composition is total valence mumber of the acidic-group of polymerizable monomer,
Said is biphosphate monoesters group and/or phosphoric acid hydrogen two ester groups by the deutero-acidic-group of phosphoric acid,
Said polyvalent metal ion release property composition (B) is earth metal compound or earth metal ion stripping property filler,
Said earth metal compound is the hydroxide or the alkoxide of earth metal,
Said earth metal is meant rare earth metal or aluminium family metal.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007038059A JP5089192B2 (en) | 2007-02-19 | 2007-02-19 | Dental adhesive composition |
| JP038059/2007 | 2007-02-19 | ||
| JP040031/2007 | 2007-02-20 | ||
| JP2007040031A JP5059443B2 (en) | 2007-02-20 | 2007-02-20 | Dental adhesive composition |
| PCT/JP2007/072145 WO2008102489A1 (en) | 2007-02-19 | 2007-11-08 | Adhesive composition for dental use |
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| Publication Number | Publication Date |
|---|---|
| CN101588782A CN101588782A (en) | 2009-11-25 |
| CN101588782B true CN101588782B (en) | 2012-12-19 |
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ID=39779572
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| CN2007800503155A Expired - Fee Related CN101588782B (en) | 2007-02-19 | 2007-11-08 | Adhesive composition for dental use |
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| CN (1) | CN101588782B (en) |
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| EP2816049B8 (en) * | 2013-06-20 | 2018-07-11 | Ivoclar Vivadent AG | ß-ketophosphonic acids and all dental materials based thereon |
| WO2018074594A1 (en) * | 2016-10-21 | 2018-04-26 | クラレノリタケデンタル株式会社 | Self-adhesive dental composite resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1273809A (en) * | 1999-05-13 | 2000-11-22 | 可乐丽股份有限公司 | Binding compsns. |
| CN1365269A (en) * | 1999-04-14 | 2002-08-21 | 宝洁公司 | Denture adhesive compositions |
| US6583197B1 (en) * | 1999-07-08 | 2003-06-24 | Kabushiki Kaisha Shofu | Dental adhesive composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3520706B2 (en) * | 1997-02-27 | 2004-04-19 | 株式会社トクヤマ | Adhesive composition |
| JP4818591B2 (en) * | 2004-03-05 | 2011-11-16 | 株式会社松風 | 1-step dental adhesive composition |
-
2007
- 2007-02-19 JP JP2007038059A patent/JP5089192B2/en active Active
- 2007-11-08 CN CN2007800503155A patent/CN101588782B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1365269A (en) * | 1999-04-14 | 2002-08-21 | 宝洁公司 | Denture adhesive compositions |
| CN1273809A (en) * | 1999-05-13 | 2000-11-22 | 可乐丽股份有限公司 | Binding compsns. |
| US6583197B1 (en) * | 1999-07-08 | 2003-06-24 | Kabushiki Kaisha Shofu | Dental adhesive composition |
Non-Patent Citations (2)
| Title |
|---|
| JP特开平10-236912A 1998.09.08 |
| JP特开平11-130465A 1999.05.18 |
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| CN101588782A (en) | 2009-11-25 |
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