CN100560629C - The stable positively charged ion approach crosslinkable/polymerisable dental composition that passes through with high filler content - Google Patents
The stable positively charged ion approach crosslinkable/polymerisable dental composition that passes through with high filler content Download PDFInfo
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- CN100560629C CN100560629C CNB2005800228426A CN200580022842A CN100560629C CN 100560629 C CN100560629 C CN 100560629C CN B2005800228426 A CNB2005800228426 A CN B2005800228426A CN 200580022842 A CN200580022842 A CN 200580022842A CN 100560629 C CN100560629 C CN 100560629C
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Abstract
The present invention relates to highly-filled positively charged ion dental composition, said composition comprises: at least a by the reactive compound of positively charged ion approach (A); At least a dental filler (B); Randomly, at least a dispersion agent (C), it comprises at least a organic polymer or multipolymer; At least a cation light initiator; Randomly, at least a photosensitizers (E), described composition is characterised in that at least a dental filler (B) is through using following mass treatment: at least a organo-silicon coupling agent (F) and at least a compound (G), described organo-silicon coupling agent (F) comprises at least one and directly is connected in active function groups (rfA) on the Siliciumatom, it forms chemical bond with the dental filler after activation, this coupling agent also comprises at least one and directly is not connected in active function groups (rfB) on the Siliciumatom, and it forms chemical bond with the active function groups (rfC) of compound (G) after activation.
Description
Technical field
The field of the invention is the field of dental composition.More particularly, the dental composition of being studied within the scope of the present invention can be used to make dental prosthesis and be used for dental prosthetic.
Background technology
These dental compositions normally Resins, epoxy, photopolymerization organosilicon or by free radical method polymerizable acrylate resin.These compositions further comprise particulate state reinforcing filler (for example, hydrophobic silicon-dioxide), light trigger and optional photosensitizers, even other functional additive such as pigment or stablizer.
In case mix, these compositions just be formed and then photo-crosslinking become to be similar to tooth main body structure body.
Filler is made of the very thin particle with high-specific surface area (≈ 0.01 to 5 μ m), this effects limit its add-on in resin.This is because the receptivity of described resin is limited.Therefore, the filler content in these compositions seldom reaches greater than 45 volume %.This thus impair the mechanical enhancement that granulated filler is given.
And, dental composition and reinforcing filler mineral glass or the preparation of combustion method silicon-dioxide as having unusual low particle size, its silane surface alcohol and/or residual water and Cationic functional groups react, thereby overslaugh the storage of composition.When utilize silane such as glycidyl oxygen base propyl trimethoxy silicane or glycidyl oxygen base propyl-triethoxysilicane or even when these glass of methacryloxypropyl trimethoxy silane pre-treatment or these combustion method silicon-dioxide, situation also is like this.Reinforcing filler interacts with the active function groups of (light) polymerizable/crosslinkable material, and this causes the instability problem of dental composition in storage process, and the storage time may reach some months.Concerning highly-filled composition (as overall filler content 〉=50%), the unsettled phenomenon of this storage strengthens.
Patent US-B-6 306 926 relates to dental composition, its based on Resins, epoxy (as
), trimethylene oxide or vinyl ether etc., they pass through positively charged ion approach polymerizable/crosslinkable under radiation condition, and randomly, by free radical approach polymerisable (methyl) acrylate resin.Except polymerisation induced agent such as cation light initiator with randomly the radical initiator, according to actual needs, these compositions can comprise radiopaque microgranular mineral filler, this mineral filler is selected from following metallic compound: oxide compound, halogenide, borate, phosphoric acid salt, silicate, carbonate, germanate, a tetrafluoro borate, hexafluorophosphate, its iso-electric point is less than 7.These compositions 25 ℃ of following cationoid polymerisations after 30 minutes Barcol hardness be 10 at least.
The shortcoming of these resins is that they not exclusively see through the actinic radiation through the reaction of UV-visible radiation activated polymerization, and this is unfavorable for reaction kinetics, and has limited the possibility that obtains very thick photo-crosslinking material thus.
Patent application FR-A-2 784 025 purposes are by proposing to solve this problem based on the dental composition of silicone resin, these silicone resins under radiation condition by positively charged ion approach polymerizable/crosslinkable, carry out subsequently or do not carry out heat afterwards-crosslinked.These silicone resins comprise oxyethane (epoxide, trimethylene oxide etc.) or vinyl ether functional degree.This composition comprises:
-one or more are by positively charged ion approach polymerizable and/or crosslinkable polydimethylsiloxane, and its at least one end has the active function groups of following formula:
At least a borate type initiator of-significant quantity:
-at least a photosensitizers and
-at least a dental or inertia reinforcing filler, these fillers are 200m based on dental glass or polymethylmethacrylate or specific surface area
2The combustion method silicon-dioxide of/g, this silicon-dioxide is optional to be handled through hexamethyldisilazane or polydimethylsiloxane.
These dental compositions are used to make dental prosthesis or the artificial utensil of dentistry and are used for dental prosthetic.
These organosilicons are better than cationic crosslinked organic resin part and are the height penetrance of UV-visible light to it, thereby can obtain to utilize the very thick material (a few mm thick) of UV lamp photo-crosslinking in the very short time (being less than 1 minute) of visible emitting scope＞400nm.
Yet, these organosilicons and the reinforcing filler with Lewis acid or Bronsted acidity matter are prepared as having very the abrading glass or the combustion method silicon-dioxide of low particle size, and silanol that it is surperficial and/or residual water and Cationic functional groups react.Instability when therefore, these silicone formulations store.And, when the preparation of the photosensitizers of these organosilicons and thioxanthone type, big colour-change appears when the radiation that is subjected to being used for photo-crosslinking.This shows as secretly rose-colored in final product (after radiation), says that from aesthstic angle this does not wish to occur.
Except that above-mentioned these problems, these organosilicon dental compositions are still expecting to be improved aspect the raising filler content, so that can improve mechanical property.
The dental composition of filling in addition by patent application EP-A-1 050 291 known altitude, it shows as the dispersion agent of the phosphoric acid ester type of filler (as combustion method silicon-dioxide) that the particle size (Φ m) that has good mechanical property and comprise 10 volume % to 70 volume % is 0.05 to 0.5 μ m (particle of diameter of phi＞0.50 μ m is less than 50 volume %), the acrylic monomer by the photopolymerization of free radical approach and following formula:
R-[-CO-(CH
2)
5-O-]
n-PO
3H
2
These instructions that relate to the free radical dental composition can not be applied to based in the organosilyl positively charged ion dental composition at all.This is because dispersion agent R-[-CO-(CH
2)
5-O-]
n-PO
3H
2Be unsuitable for cation composition, particularly because they comprise a large amount of acidic residues RPO
3H
2, it reacts and damages the stability of composition under the condition that oxyethane functional group exists.
Therefore as can be seen, at stability in storage and the dual problem of mass filler dispersive in resin based on the dental composition by the polymerisable unit of positively charged ion approach (for example oxyethane) under the UV condition, prior art does not propose gratifying solution.And prior art also proposes solution less than the remaining coloring problem after crosslinked at dental composition.
Summary of the invention
One of main purpose of the present invention is to solve the problems referred to above by proposing new dental composition, this dental composition based under the UV condition by the polymerisable unit of positively charged ion approach (as oxyethane), and can not occur in the prior art and stability in storage and the limited relevant defective of filler content.
Another main purpose of the present invention provides polymerizable and/or crosslinkable novel cation dental composition in oral environment, it is stable storing and highly-filled (as 〉=50%) not only, but also have the advantage that UV-visible light height is seen through, therefore can use the UV lamp of visible emitting＞400nm scope in the very short time (being less than 1 minute), to obtain very thick photo-crosslinking material (a few mm thick).
Another main purpose of the present invention provides polymerizable and/or crosslinkable novel cation dental composition in oral environment, it is stable, highly-filled (as 〉=50%) is easy to preparation and economy, and does not produce the painted defective of interference after crosslinked.
Another main purpose of the present invention provides a kind of novel method that is used to handle reinforcing filler, particularly dental reinforcing filler of this reinforcing filler, and when it was particularly useful as reinforcing filler in the dental composition, it can satisfy above-mentioned requirements.
These purposes wherein can realize that the present invention at first relates to a kind of dental composition by the present invention, and said composition comprises:
(1) at least a by the reactive compound of positively charged ion approach (A);
(2) at least a dental filler (B);
(3) randomly, at least a dispersion agent (C), it comprises at least a organic polymer or multipolymer;
(4) at least a cation light initiator (D);
(5) and randomly, at least a photosensitizers (E),
Described composition is characterised in that at least a dental filler (B) is through using following mass treatment:
A) at least a organo-silicon coupling agent (F) and
B) at least a compound (G),
Described organo-silicon coupling agent (F) comprises that the active function groups (rfC) that directly is connected in active function groups (rfA) on the Siliciumatom and at least one and compound (G) of at least one and the reaction of this dental filler reacts directly is not connected in active function groups (rfB) on the Siliciumatom.
One preferred embodiment in:
-the active function groups (rfA) that directly is connected on the Siliciumatom of organo-silicon coupling agent (F) is an alkoxyl group, alkene oxygen base (enoxy) or hydroxy functional group;
-the active function groups (rfB) that directly is not connected on the Siliciumatom of organo-silicon coupling agent (F) is an oxyethane, trimethylene oxide, hydroxyl, acid, carboxylic acid anhydride or functionalized with glycols group; With
The active function groups (rfC) of-compound (G) is an oxyethane, trimethylene oxide, alkenyl ether or carbonate functionalities.
The inventor's contribution is, and is wondrous and find unexpectedly, can handle filler the surface and thereby improve filler content, thus can be when improving the stability in storage of composition strongthener.This stability means the storage time of some months or several years.
Because this technical scheme is an economically feasible and easy to implement, thereby it is more favourable.
Equally advantageously, be gratifying aspect the contraction of this composition after limit polymerization/crosslinked, this is considerable in dental applications.
According to a preferred variation of the present invention, dental composition of the present invention comprises at least a dental filler (B), and this filler (B) has passed through the processing of the method (I) that comprises the following steps:
A) with dental filler (B) and at least a organo-silicon coupling agent (F) in solvent medium, preferably in water-bearing media, mix, this organo-silicon coupling agent (F) comprises at least one and directly is connected in alkoxyl group on the Siliciumatom and/or hydroxy functional group and at least one oxyethane, trimethylene oxide, hydroxyl, acid, carboxylic acid anhydride and/or functionalized with glycols group
B) evaporation removes to desolvate and obtains middle dental filler (B-1),
C) heat-treat this centre dental filler (B-1), so that carry out linked reaction between middle dental filler (B-1) and the coupling agent (F), and dental filler (B-2) in the middle of obtaining thus,
D) then in solvent medium middle dental filler (B-2) is mixed with at least a compound (G), this compound (G) comprises at least one oxyethane, trimethylene oxide, and alkenyl ether and/or carbonate functionalities,
E) evaporation remove desolvate obtain in the middle of dental filler (B-3) and
F) heat-treat this centre dental filler (B-3), so that react between middle dental filler (B-3) and the compound (G), obtains treated dental filler (B-4) thus.
According to another preferred variation of the present invention, step c) and f in the method (I)) thermal treatment be less than or equal to 200 ℃ by being heated to, preferably be less than or equal to 165 ℃, more preferably 100 to 165 ℃ temperature is carried out.
According to a preferred embodiment of the present invention, with respect to the gross weight of dental composition, the total content of dental filler (B) is up to 85 weight %, preferred 60 weight % to 80 weight %.
Advantageously, the processing of dental filler (B) is to use with respect to the dental composition gross weight to being up to 20 weight %, preferred 1 weight % to 15 weight %, and more preferably the compound (G) of 2 weight % to 10 weight % carries out.
Utilize the processing of the dental filler (B) of organo-silicon coupling agent (F) preferably to utilize the compound of following formula to carry out:
Wherein:
-R is the C1-C4 alkyl or the alkenyl of hydrogen or linearity or branching,
-R
1Be the alkyl or the phenyl of linearity or branching,
-x equals 0,1 or 2, and
X is defined by following structural:
Wherein:
-E and D are identical or different groups, are selected from the C1-C12 alkyl of linearity or branching,
-z is 0 or 1,
-n is 0 or 1,
-p is 0,1,2,3,4,5 or 6;
-R
2, R
3, R
4, R
5, R
6, R
7And R
8Be identical or different group, the C1-C12 alkyl of expression hydrogen atom or linearity or branching.
The preferred organo-silicon coupling agent (F) that can enumerate comprises following compounds: glycidyl oxygen base propyl trimethoxy silicane, the hydrolysate of glycidyl oxygen base propyl trimethoxy silicane; Glycidyl oxygen base propyl-triethoxysilicane, the hydrolysate of glycidyl oxygen base propyl-triethoxysilicane in acidic medium; Glycidyl oxygen base propyl group dimethoxy-methyl silane or its hydrolysate, silane β-(3,4-epoxy group(ing) cyclohexyl) ethyl triethoxysilane or its hydrolysate, silane β-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane or its hydrolysate.
Utilize the processing of the dental filler (B) of compound (G) preferably to utilize a kind of compound to carry out, this compound is to comprise at least one oxyethane, trimethylene oxide, alkenyl ether and/or carbonate functionalities and even more preferably comprise the organic monomer of at least one oxyethane functional group, oligopolymer or polymkeric substance or organosilicon oxidation alkane.
Preferably, compound (G) comprises at least one and is selected from following (M-7) functional group to structure shown in (M-12):
(M-11)
-(CH
2)
3-O-CH＝CH
2；
(M-12)-(CH
2)
3-O-CH＝CH-R″
" the C1-C6 alkyl group of expression linearity or branching of R wherein.
According to first preferred embodiment, compound (G) is organosilicon oligopolymer (G-1) or organosilicon polymer (G-2).Organosilicon oligopolymer (G-1) or organosilicon polymer (G-2) comprise:
A) at least a unit of following formula:
Wherein:
-a=0,1 or 2,
-R
0, identical or different, the expression alkyl, cycloalkyl, aryl, vinyl, hydrogen or alkoxy base, preferred C1-C6 low alkyl group,
-Z, identical or different, the expression contain at least one oxyethane, alkenyl ether, the organic substituent of trimethylene oxide and/or carbonate functionalities and
B) at least two Siliciumatoms.
Advantageously, organosilicon oligopolymer (G-1) or organosilicon polymer (G-2) are selected from the compound shown in the following structural:
L=H wherein; OH; Me; Phenyl; The C1-C12 alkyl; The C1-C6 cycloalkyl; Following radicals:
Perhaps
N＜100 wherein; A＜100 and m＜100
N＜100 wherein
(S-15)
In these structural formulas, R
0Or R
0Be identical or different, expression alkyl, cycloalkyl or aromatic yl group, preferred C1-C6 low alkyl group.
In these structural formulas, group D is that the C1-C12 alkyl of linearity or branching and n are the integer (comprising end value) between 1 to 20, wherein Ar=aromatic yl group.
According to second preferred embodiment, compound (G) is the silane shown in the following formula (G-3):
In this structural formula:
-R, identical or different, the expression alkyl, cycloalkyl, aryl, vinyl, hydrogen or alkoxy base, preferred C1-C6 low alkyl group,
-Z, identical or different, expression comprises at least one oxyethane, alkenyl ether, the organic substituent of trimethylene oxide and/or carbonate functionalities, and
-a+b＝3。
According to one preferred embodiment, silane (G-3) is selected from molecule (S-93) to (S-95):
According to another preferred embodiment, compound (G) is the organic compound (G-4) that is selected from molecule (S-96) to (S-104):
In these structural formulas: n is the integer (comprising end value) between 1 to 10:
The C1-C12 alkyl of n＜100 and D=linearity or branching wherein.
In the molecule of (S-103) type, can select the resin of selling by DOW CHEMICAL company
The C1-C12 alkyl of n＜100 and group D=linearity or branching wherein.
For the resin of (S-104) type, wherein the resin of n=0 is particularly suitable for the present invention.
Usually, the photochemistry activation is carried out under the UV radiation.More particularly, the UV radiation of wavelength about 200 to 500nm is used to prepare dental prosthesis, and wavelength is used to prepare repair materials greater than the UV-visible radiation of 400nm.Wavelength greater than 400nm makes it possible to take place crosslinked and/or polymerization in oral environment.
Photochemical (photochemistry) activation can advantageously be finished (perhaps even with thermal activation replacing) with thermal activation.
Preferably, be selected from by the reactive compound of positively charged ion approach (A) and comprise Resins, epoxy, vinyl ether, trimethylene oxide, spiro original magnesium ester, the monomer of spiral shell original carboxylic acid ester (spiro-orthoesters) and their combination and/or (being total to) polymkeric substance.
More preferably, be organosilicon oligopolymer (G-1) by the reactive compound of positively charged ion approach (A), organosilicon polymer (G-2), silane (G-3) or the organic compound (G-4) that defines by said units (M-13), or molecule (S-1) is to (S-101).
In formula (M-13), particularly advantageous active function groups Z comprises the active function groups that at least one is selected from following groups:
(R-8)：
-(CH
2)
3-O-CH＝CH
2；
(R-9)：-(CH
2)
3-O-CH＝CH-R″
" the C1-C6 alkyl group of expression linearity or branching of R wherein.
According to a favourable version, combine with organic Resins, epoxy or trimethylene oxide less than 80% massfraction by the reactive compound of positively charged ion approach (A).In the functionality organic resin of selecting, preferably its active function groups mass percent is less than 20%, preferably less than 15% resin.Volumetric shrinkage in the polymerization process will reduce more.
Preferred selecting type (S-103) and resin (S-104):
The C1-C12 alkyl of n＜100 and D=linearity or branching wherein.
In the resin of (S-103) type, the resin that can select DOW CHEMICAL company to sell
The C1-C12 alkyl of n＜100 and group D=linearity or branching wherein.
For the resin of (S-104) type, wherein the resin of n=0 is particularly suitable for the present invention.
Dissimilar dental fillers (B) can be used for preparing composition of the present invention.These fillers are selected according to the end-use of dental composition: the important performance of they influences, as outward appearance, UV radiating penetrance, and dental composition is crosslinked and/or polymerization after the machinery and the physicals of the material that obtains.
As reinforcing filler, can use treated or untreated pyrogenic silica filler, the soft silica filler, quartzy, glass or non-vitreous filler, this non-vitreous filler is based on those types (not having barium) of describing among silicon oxide such as the US 6297181, zirconium white, barium oxide, calcium oxide, oxyfluoride, aluminum oxide, titanium oxide, zinc oxide, borosilicate, silico-aluminate, talcum, Spherosil (spherosil), three fluoridize ytterbium, based on polymkeric substance such as the inertia or the functionalized poly methyl methacrylate of abrasive flour form, the filler of polyepoxide or polycarbonate, ceramic whisker (Si-C, Si-O-C, Si-N, Si-N-C, Si-N-C-O), glass fibre.
Can enumerate following material as an example:
-based on the inert filler of polymethylmethacrylate
, UGL company, can be used for dental field and be colored as rose-colored,
The specific surface area that-polydimethylsiloxane or hexamethyldisilazane are handled is 200m
2The combustion method silica filler of/g,
-untreated combustion method silica filler (AEROSIL
, DEGUSSA company sells),
-quartzy or based on the glass of silicon oxide.
According to the embodiment of the present invention, dental filler (B) is unorganic glass or combustion method silicon-dioxide.
According to a favourable feature of the present invention, with respect to the gross weight of dental composition, dental filler (B) is up to 85 weight %, is preferably 50 to 85 weight %, more preferably 60 to 85 weight %.
According to the present invention, dispersion agent (C) is selected from: randomly by the salifiable polyurethane/acrylate multipolymer of alkylammonium, randomly by the salifiable acrylic copolymer of alkylammonium, single diester of carboxylic acid, polyester, polyethers, urethane, the urethane of modification, polyvalent alcohol-polyacrylic ester, the multipolymer of above-mentioned substance or mixture.With trade mark
(Byk company) or
The dispersion agent that (Avecia company) sells is specially adapted to the present invention.Especially and as an example, can enumerate commodity:
Can also be set forth in the dispersion agent of mentioning in the following patent:
-patent US-B-5,882,393 have described the dispersion agent based on urethane/imidazoles-acrylate or epoxide;
-patent US-B-5,425,900 have described the dispersion agent based on urethane;
-patent US-B-4,795,796 have described the dispersion agent based on urethane/polyoxyalkylene glycol monoalky lether;
-patent application WO-A-99/56864 has described the dispersion agent based on urethane/poly-(alkylidene oxide-carbonyl): it is derived from 6-caprolactone and δ-Wu Neizhi; With
-patent EP-B-0 403 197 has described grafted polyvalent alcohol-polyacrylate dispersion agent, and it comprises urethane/polyvinyl/polyacrylic ester random copolymers and polyoxyalkylene polyethers.
Say that quantitatively the ratio of dispersion agent (C) is 50ppm to 1%, preferred 100ppm to 5000ppm.
Preferably, the amine index of dispersion agent (C) is less than or equal to 60, more preferably 0.1 to 50mg potassium hydroxide/gram dispersion agent (C).
Advantageously, the acid number of dispersion agent is less than or equal to 200, preferably is less than or equal to 100, more preferably 1 to 60mg potassium hydroxide/gram dispersion agent.
Cation light initiator (D) is selected from the periodic table of elements [Chem.﹠amp; Eng.News, vol.63, N ° of on February 4th, 5,26,1985] borate of the borate (using separately or with form of mixtures) of 15 to 17 family's elements or the organometallic complex of the periodic table of elements [identical reference] 4 to 10 family's elements.
According to preferred embodiment a kind of, cation light initiator (D) be the borate type and be selected from such material, for this material:
A) boratory cationic moiety is selected from:
(1) salt of following formula:
[(R
9)
n-A-(R
10)
m]
+ (I)
Wherein:
-A represents 15 to 17 family's elements, I for example, and S, Se, P or N,
-R
9Expression C6-C20 heterocycle or carbon ring aromatic yl group, described heterocyclic group can comprise nitrogen or the assorted element of sulphur conduct,
-R
10Expression R
9Or the alkyl of C1-C30 linearity or branching or kiki alkenyl group; Described radicals R
9And R
10Randomly by the C1-C25 alkoxyl group, the C1-C25 alkyl, nitro, chlorine, bromine, cyano group, carboxyl, ester group or sulfydryl replace,
-m and n are integers, n+m=v+1 wherein, and v is the valency of elements A,
(2) the different sulfo-chroman of specifically described oxo (oxoisothiochromanium) salt among the patent application WO90/11303, the particularly sulfonium salt of different sulfo-chroman of 2-ethyl-4-oxo or 2-dodecyl-different sulfo-chroman of 4-oxo, and the different sulfo-chroman of the oxo shown in structural formula V salt:
Structure V
Wherein:
A represents:
The integer of n1=1 to 3;
The integer of z1=0 to 3;
X expression M
1Y
1 R1(1) or formula Q
1(2) group is wherein at M
1Y
1 R1(1) in: M
1=Sb, As, P, B or Cl,
Y
1Expression halogen (preferred F or Cl) or O and wherein r1 be 4 to 6 integer, formula Q
1(2) expression sulfonic acid,
R
81-SO
3, R wherein
81Be the alkyl or aryl group, perhaps by the alkyl or aryl group of preferred F of halogen or Cl replacement,
R
101Expression alkyl or cycloalkyl group, preferred C1-C20 perhaps represents aromatic yl group,
R
21Expression hydrogen, alkyl, alkenyl, cycloalkenyl group or cycloalkyl, preferred C1-C20 perhaps represents aryl, all R
21Be independently each other,
R
31Expression hydrogen, alkyl, alkenyl, cycloalkenyl group or cycloalkyl, preferred C1-C20 perhaps represents aryl, all R
31Be independently each other,
R
41Expression hydrogen, halogen, alkenyl such as vinyl, cycloalkenyl group, alkyl or cycloalkyl, preferred C1-C20 perhaps represents alkoxyl group or thio alkoxy, preferred C1-C20, perhaps expression has and is up to 10 alkylene oxide units and by end capped poly-(alkylene oxide) group of hydroxyl or alkyl (C1-C12), or aryl, or aryloxy, or thio-aryloxy
R
51The expression halogen, alkenyl such as vinyl, perhaps cycloalkenyl group, alkyl or cycloalkyl, preferred C1-C20, perhaps represent alkoxyl group or thio alkoxy, preferred C1-C20, perhaps expression has and is up to 10 alkylene oxide units and by hydroxyl or end capped poly-(alkylene oxide) group of alkyl (C1-C12), or aryl, or aryloxy, or thio-aryloxy
R
61Expression hydrogen, alkyl, alkenyl, cycloalkenyl group or cycloalkyl, preferred C1-C20 perhaps represents aryl,
R
71Expression hydrogen, alkyl, alkenyl, cycloalkenyl group or cycloalkyl, preferred C1-C20, perhaps represent aryl and
(3) organic metal salt as follows:
(L
1L
2L
3M)
+q (II)
Wherein:
-M represents 4 to 10 family's metals, particularly iron, manganese, and chromium or cobalt,
-L
1Expression is by 1 part of πDian Zi and metal M keyed jointing, and this part is selected from η
3-alkyl, η
5-cyclopentadienyl and η
7-cycloheptatriene ylidene ligands and η
6-aromatics, this compound are selected from the optional η that replaces
6-benzene part and compound with 2 to 4 condensed ring, each ring can be contributed the valence shell of metal M by 3 to 8 πDian Zis,
-L
2Expression is by the part of πDian Zi and metal M keyed jointing, and this part is selected from η
7-cycloheptatriene ylidene ligands and η
6-aromatics, this compound are selected from the optional η that replaces
6-benzene part and compound with 2 to 4 condensed ring, each ring can be contributed the valence shell of metal M by 6 or 7 πDian Zis,
-L
3Expression is by 0-3 identical or different part of σDian Zi and metal M keyed jointing, and this part is selected from CO and NO2+, L
1, L
2And L
3With the ionic charge contribution of metal M to total elementary charge q of title complex for just and be 1 or 2; With
B) borate anion partly has structural formula:
[BX
aR
b]
- (III)
Wherein:
-a is 0 to 3 integer, and b is 1 to 4 integer, a+b=4 wherein,
-symbol X represents:
* halogen atom (chlorine, fluorine), a=0 to 3 wherein, perhaps
* OH functional group, a=0 to 2 wherein,
-symbol R is identical or different, and:
-when cationic moiety was the positively charged ion of 15 to 17 family's elements, R represented by at least a electron-withdrawing group such as OCF
3, CF
3, NO
2, CN and/or the phenyl that is replaced by at least two halogen atoms (particularly fluorine atom),
-when cationic moiety was the organometallic complex of 4 to 10 family's elements, R represented by the phenyl of at least a electrophilic element or group replacement, particularly by halogen atom (especially fluorine atom), CF
3, OCF
3, NO
2, CN replaces, or
-no matter be any cationic moiety, R represents to comprise the aryl such as the xenyls of at least two virtue nuclears, naphthyl, it is optional to be replaced by at least a electrophilic element or group, particularly by halogen atom, fluorine especially, OCF
3, CF
3, NO
2, CN replaces.
Without limitation, will further introduce the preferred especially within the scope of the invention borate that uses and the subclass of organic metal borate in detail below.
According to first preferred version of the present invention, the kind of particularly suitable borate anion part is as follows:
1′：[B(C
6F
5)
4]
- 5′：[B(C
6H
3(CF
3)
2)
4]
-
2′：[(C
6F
5)
2BF
2]
- 6′：[B(C
6H
3F
2)
4]
-
3′：[B(C
6H
4CF
3)
4]
- 7′：[C
6F
5BF
3]
-
4′：[B(C
6F
4OCF
3)
4]
-
According to second preferred version of the present invention, the salt of operable formula (S-26) is described in a large amount of documents, is recorded in patent US-A-4 026 705 especially, and US-A-4 032 673, US-A-4 069 056, among US-A-4 136 102 and the US-A-4 173 476.Therein, preferred more especially following positively charged ion:
[(C
8H
17)-O-(C
6H
4)-I-C
6H
5)]
+；[C
12H
25-(C
6H
4)-I-C
6H
5]
+；
[(C
8H
17-O-(C
6H
4))
2I]
+；
[(C
8H
17)-O-(C
6H
4)-I-C
6H
5)]
+；[(C
6H
5)
2S-(C
6H
4)-O-C
8H
17]
+；
[CH
3-C
6H
4-I-C
6H
4-CH
2CH(CH
3)
2]
+；
[(C
12H
25-(C
6H
4)-I-(C
6H
4)-CH-(CH
3)
2]
+；[(C
12H
25-C
6H
4)
2I]
+；
[(C
6H
5)
3S]
+；[CH
3-(C
6H
4)-I-(C
6H
4)-CH(CH
3)
2]
+；
(η
5-cyclopentadienyl) (η
6-toluene) Fe
+
(η
5-cyclopentadienyl) (η
6-isopropyl benzene) Fe
+
(η
5-cyclopentadienyl) (η
6-1-methylnaphthalene) Fe
+
[(C
6H
5)-S-C
6H
4-S-(C
6H
5)
2]
+；[(CH
3-(C
6H
4)-I-(C
6H
4)-OC
2H
5]
+；
[(C
nH
2n+1-C
6H
4)
2I]
+(wherein for group C
nH
2n+1, n=1 to 18, and be linearity or branching).
According to the 3rd preferred version, the organic metal salt (3) of operable formula (S-27) is recorded in document US-A-4 973 722, and US-A-4 992 572, and EP-A-203 829, among EP-A-323584 and the EP-A-354 181.The organic metal salt of the more pleased employing of the present invention is specifically:
(η
5-cyclopentadienyl) (η
6-toluene) Fe
+
(η
5-cyclopentadienyl) (η
6-1-methylnaphthalene) Fe
+
(η
5-cyclopentadienyl) (η
6-isopropyl benzene) Fe
+
Two (η
6-
) Fe
+
Two (η
6-benzene) Cr
+
According to these three preferred versions,, can enumerate following products as the example of borate type light trigger:
(P-16)：[(C
8H
17)-O-C
6H
4-I-C
6H
5)]
+，[B(C
6F
5)
4]
-；
(P-17)：[C
12H
25-C
6H
4-I-C
6H
5]
+，[B(C
6F
5)
4]
-；
(P-18)：[(C
8H
17-O-C
6H
4)
2I]
+，[B(C
6F
5)
4]
-；
(P-19)：[(C
8H
17)-O-C
6H
4-I-C
6H
5)]
+，[B(C
6F
5)
4]
-；
(P-20)：[(C
6H
5)
2S-C
6H
4-O-C
8H
17]
+，[B(C
6H
4CF
3)
4]
-；
(P-21)：[(C
12H
25-C
6H
4)
2I]
+，[B(C
6F
5)
4]
-；
(P-22)：[CH
3-C
6H
4-I-C
6H
4-CH(CH
3)
2]
+，[B(C
6F
5)
4]
-；
(P-23): (η
5-cyclopentadienyl) (η
6-toluene) Fe
+, [B (C
6F
5)
4]
-
(P-24): (η
5-cyclopentadienyl) (η
6-1-methylnaphthalene) Fe
+, [B (C
6F
5)
4]
-
(P-25): (η
5-cyclopentadienyl) (η
6-isopropyl benzene) Fe
+, [B (C
6F
5)
4]
-
(P-26)：[C
12H
25-C
6H
4)
2I]
+，[B(C
6H
3(CF
3)
2]
-；
(P-27)：[CH
3-C
6H
4-I-C
6H
4-CH
2CH(CH
3)
2]
+，[B(C
6F
5)
4]
-；
(P-28): [CH
3-C
6H
4-I-C
6H
4-CH
2CH (CH
3)
2]
+, [B (C
6H
3(CF
3)
2)
4]
-With
(P-29)：[CH
3-C
6H
4-I-C
6H
4-CH(CH
3)
2]
+，[B(C
6H
3(CF
3)
2)
4]
-。
As other reference of definition borate (1) and (2) and organic metal borate (3), can enumerate the full content of patent application EP 0 562 897 and 0 562 922.These contents all are incorporated in this explanation by reference.
Other example as being used as the salt of light trigger can be set forth in those disclosed among U.S. Pat 4 138 255 and the US 4 310 469.
Also can use other cation light initiator, for example:
-phosphofluoric acid salt compounded of iodine or hexafluoro-antimonic acid salt compounded of iodine, as:
-[CH
3-[(C
6H
4)-I-[(C
6H
4)-CH(CH
3)
2]
+[PF
6]
-；
-[CH
3-(C
6H
4)-I-(C
6H
4)-CH
2CH(CH
3)
2]
+[PF
6]
-；
-[(C
12H
25-C
6H
4)
2I]
+[PF
6]
-Or
The ferrocene salt of-these different anions.
The photosensitizers that comprises in the dental composition of the present invention can have very different character.Within the scope of the invention, it is especially corresponding to the material of following formula (IV) to one of formula (XXIV):
Structural formula (IV)
Wherein:
-when n=1, Ar
1Expression contains the aromatic yl group of 6 to 18 carbon atoms, tetralyl, and thienyl, pyridyl or furyl group perhaps have one or more substituent phenyl, and described substituting group is selected from F, Cl, Br, CN, OH, the C1-C12 alkyl of linearity or branching ,-CF
3,-OR
13,-O phenyl ,-SR
13,-S phenyl ,-SO
2Phenyl ,-COOR
13,-O-(CH
2-CH=CH
2) ,-O (CH
2H
4-O)
m-H ,-O (C
3H
6O)
m-H, m are 1 to 100,
-when n=2, Ar
1Expression C6-C12 arylene group or phenylene-T-phenylene group, wherein T represents-O-,-S-,-SO
2-or-CH
2-,
-X represents-OR
14Or-OSiR
15(R
16)
2Or and R
11Formation-O-CH (R
17)-,
-R
11Represent unsubstituted or have-OH-OR
13, C2-C8 acyloxy ,-CF
3Or-linearity or the branching C1-C8 alkyl group of CN group, C3 or C4 kiki alkenyl group, C6 to C18 aromatic yl group or C7 to C9 phenylalkyl group,
-R
12Has R
11One of definition, perhaps expression-CH
2CH
2R
18Group, perhaps selectively with R
11Form C2-C8 alkylidene group or C3-C9 oxa-alkylidene group or azepine alkylidene group together,
-R
13Expression comprises the low alkyl group of 1 to 12 carbon atom,
-R
14The expression hydrogen atom, the C1-C12 alkyl has-OH-OR
13Or the C2-C6 alkyl of CN, the C3-C6 alkenyl, cyclohexyl or benzyl, the optional phenyl that is replaced by the C1-C12 alkyl of chlorine atom or linearity or branching, perhaps 2-THP trtrahydropyranyl,
-R
15And R
16Be identical or different, represent the C1-C4 alkyl or phenyl separately,
-R
17The expression hydrogen atom, the C1-C8 alkyl or phenyl,
-R
18Expression-CONH
2,-CONHR
13,-CON (R
13)
2,-P (O) (OR
13)
2Or 2-pyridyl:
The structure formula V
Wherein:
-Ar
2Have with formula (IV) in Ar during n=1
1Identical implication,
-R
19Expression is selected from following group: group Ar
2, the C1-C12 alkyl of linearity or branching, the C6-C12 cycloalkyl and with the carbon atom or the group Ar of ketone
2Carbon atom form the cycloalkyl of C6-C12 ring, these groups can be selected from by one or more-F ,-Cl ,-Br ,-CN ,-OH ,-CF
3,-OR
13,-SR
13,-COOR
13Substituting group replace, optionally have-OH-OR
13And/or-linearity of CN or the C1-C12 alkyl of branching, and the C1-C8 alkenyl of linearity or branching;
Structural formula (VI)
Wherein:
-R
12, identical or different, have with formula (IV) in identical implication,
-Y, identical or different, expression X and/or R
4,
-Z represents:
Direct key,
The C1-C6 divalent alkyl, perhaps phenylene, diphenylene or phenylene-T-phenylene (T: the C1-C12 alkyl of linearity or branching), perhaps selectively with two substituent R
12And have these substituent two carbon atoms and form pentamethylene or hexanaphthene nuclear,
Divalent group-O-R
19-O-,-O-SiR
15R
16-O-SiR
15R
16-O-or-O-SiR
15R
16-O-,
-R
20Expression C2-C8 alkylidene group, C4-C6 alkylene group or xylylene,
-or selectively, following substances:
Correspondence-O-O-
-and Ar
4Have with formula (IV) in Ar during n=1
1Identical implication.
● the thioxanthene ketone shown in the formula (VII):
-m=0 to 8,
-R
21Can be substituting group identical or different on the aromatic proton, the C1-C12 alkyl of expression linearity or branching, C6-C12 cycloalkyl, Ar
1Group, halogen atom or-OH ,-OR
13,-CN ,-NO
2,-COOR
13,-OCOR
13,-N (R
13)
2,-O-R
13-(NR
13)
2-CHO ,-O-phenyl ,-CF
3,-SR
13,-S-phenyl ,-SO
2-phenyl ,-O-alkenyl or-Si (R
13)
3
● the xanthene class shown in the formula (VIII):
N=0 to 8
● the xanthene ketone shown in the formula (IX):
P=0 to 8
● the naphthalene class shown in the formula (X):
Q=0 to 8
● the anthracene class shown in the formula (XI):
R=0 to 10
● the luxuriant and rich with fragrance class shown in the formula (XII):
S=0 to 10
● the pyrene class shown in the formula (XIII):
T=0 to 10
● the fluorenes class shown in the formula (XIV):
U=0 to 9
● the fluoranthene class shown in the formula (XV):
V=0 to 10
● shown in the formula (XVI)
Class:
W=0 to 12
● the fluorones shown in the formula (XVII):
X=0 to 8 wherein, for example 2,7-dinitrobenzene-9-Fluorenone.
● the chromone class shown in the formula (XVIII):
Y=0 to 6
● the eosin class shown in the formula (XIX):
Z=0 to 5 z=0 to 6
● the tetraiodofluorescein class shown in the formula (XX):
Z=0 to 2 or 0 to 3
● the tetraiodofluorescein class shown in the formula (XXI):
Z=0 to 3
● the temparin class shown in the formula (XXII):
X=0 to 8
● the thioxanthene ketone shown in the formula (XXIII):
Y=0 to 6
● the thioxanthene ketone shown in the formula (XXIV):
Y=0 to 6
For structural formula (VIII) to (XXIII), radicals R
21Have with at the identical definition of molecule (VII).
Can use other sensitizing agent.Can use document US 4 939 069 especially; US4 278751; The photosensitizers of describing among the US4 147 552, and be selected from tonka bean camphor, conjugation diketone, fluorone, keto-amine and the compound of right-amino-benzene vinyl ketones and their mixture.
According to a preferred mode, photosensitizers (E) is selected from anthracene, thioxanthone, the compound of camphorquinone and phenanthrenequione class and their mixture.
According to another optimal way, this dental composition comprises the thioxanthone salt that replaced by at least a group that comprises ammonium functional group as photosensitizers (E).When dental composition is crosslinked when being used to prepare dental prosthesis, use such photosensitizers to have and avoid interference painted advantage.
According to first kind of version of the present invention, utilize the association negatively charged ion of the thioxanthone salt that at least a group that comprises ammonium functional group replaces to be selected from following negatively charged ion:
-halogen root, BF
4 -, PF
6 -SbF
6 -Formula [BX as defined above
aR
b]
-Shown negatively charged ion (III), R
fSO
3 -(R
fSO
2)
3C
-Or (R
fSO
2)
2N
-, R wherein
fBe the alkyl of linearity or branching, it is by at least one halogen atom, and preferred fluorine atom replaces.
According to second kind of version of the present invention, randomly with at least a camphorquinone, the anthracene bonded photosensitizers (E) of phenanthrenequione and/or replacement has following structural:
(XXV)
Wherein:
-R
22And R
23Be identical or different, expression hydrogen or the optional C1-C10 alkyl that replaces, preferred R
22=R
23=methyl,
-(X
-) be anionic species, preferred halogen root; BF
4 -, PF
6 -SbF
6 -Formula [BX as defined above
aR
b]
-Negatively charged ion (III), R
fSO
3 -(R
fSO
2)
3C
-Or (R
fSO
2)
2N
-, R wherein
fBe the alkyl of linearity or branching, it is by at least one halogen atom, and preferred fluorine atom replaces, even more preferably (X
-) be selected from the borate of following formula: [B (C
6H
3(CF
3)
2)
4]
-[B (C
6F
5)
4]
-
According to a kind of preferred mode, randomly with at least a camphorquinone, the anthracene bonded photosensitizers (E) of phenanthrenequione and/or replacement has following structural:
Perhaps
Within the scope of the invention, photosensitizers have be used to make dental prosthesis 200 to 500nm, the remnants of preferred 400 to 500nm UV light absorb.For dental prosthetic, the photosensitizers with remnants absorption of the UV light that is higher than 400nm is preferred.
According to a kind of preferred version, photosensitizers is selected from (VII), (X), and (XI), (XIII), (XXIII), (XXIV) and (XXV) those photosensitizerss of class.According to another embodiment, photosensitizers is selected from following compounds:
-(PS-30): trimethyl ammonium chlorination 3-(3,4-dimethyl-9-oxo-9-thioxanthene-2-base-oxygen base)-2-hydroxypropyl);
-(PS-31): trimethyl ammonium four (pentafluorophenyl group) boric acid 3-(3,4-dimethyl-9-oxo-9-thioxanthene-2-base-oxygen base)-2-hydroxypropyl);
-(PS-32): trimethyl ammonium four (two (trifluoromethyl) phenyl) boric acid 3-(3,4-dimethyl-9-oxo-9-thioxanthene-2-base-oxygen base)-2-hydroxypropyl);
-(PS-33): phenanthrenequione;
-(PS-34): camphorquinone;
-(PS-35): acenaphthenequinone;
-(PS-36): dibenzoyl peroxide;
-(PS-37): 2-ethyl-9,10-dimethoxy anthracene;
-(PS-38): 9,10-diethoxy anthracene;
-(PS-39): 9,10-dibutoxy anthracene;
-(PS-40): 9-methylol anthracene;
-(PS-41): 2-dimethylamino thioxanthone;
-(PS-42): 3-ethyl carboxyl-7-methoxyl group thioxanthone;
-(PS-43): 1-phenyl sulfo--4-propoxy-thioxanthone;
-(PS-44): 2-methoxyl group thioxanthone;
-(PS-45): 2-(N, N-diethylamino propoxy-) thioxanthone;
-(PS-46): the 2-isopropyl thioxanthone;
-(PS-47): 1-chloro-4-propoxy-thioxanthone;
-(PS-48): the 4-isopropyl thioxanthone;
-and the mixture of above-mentioned substance.
Within the scope of the invention, the crosslinked stability in storage of gained material afterwards, physical strength, Young's modulus and compressive strength are obviously improved.When the thioxanthone of the described type of use formula (XXV), using randomly and at least a camphorquinone, the anthracene bonded thioxanthone (PS-31) of phenanthrenequione and/or replacement or (PS-32) time is also found an extra advantage, does not promptly exist remaining painted.
Except reinforcing filler, can also use according to required purposes and race to be used to the pigment that makes dental composition painted.
For example, for the dental composition that is used to prepare dental prosthesis, can in the presence of primitive fiber, use red pigment with simulated blood vessel.
For the dental composition that is used to prepare repair materials, also can use pigment, to obtain eburneous cross-linked material based on metal oxide (ferric oxide and/or titanium oxide and/or aluminum oxide and/or zirconium white etc.).
In dental composition of the present invention, also can introduce other additive.Biological example agent for killing, stablizer, flavouring agent, softening agent and adhesion promotor.
In the additive of being considered, advantageously use the crosslinkable and/or the polymerisable co-reactant of organic type.But these co-reactants are in a liquid state at ambient temperature or be hot melt being lower than under 100 ℃ of temperature, and every kind of co-reactant comprises at least two kinds of reactive functional groups, as trimethylene oxide-alkoxyl group, and trimethylene oxide-hydroxyl, trimethylene oxide-alkoxysilyl, carboxyl-trimethylene oxide, trimethylene oxide-trimethylene oxide, alkenyl ether-hydroxyl, alkenyl ether-alkoxysilyl, epoxy-alkoxyl group, epoxy-alkoxysilyl, dioxolane-dioxolane-alcohol.Can also enumerate for example resin R70 and R71.
Dental composition of the present invention can be used for the field of many dental applications, particularly dental prosthesis, the field of dental prosthetic and the field of temporarily using tooth.
Dental composition of the present invention is preferably the form (" single component ") of the single product that comprises different components, and this helps using, particularly in the field of dental prosthesis.If desired, the organic derivative with amine functional group that can utilize document WO 98/07798 to be instructed guarantees the stability of product.
In the field of dental prosthesis, the product of " single component " form can by syringe directly be deposited on the plaster mold or tooth wedge (cl é) in.Make its polymerization (carrying out polymerization) by UV lamp (visible spectrum 200-500nm) then by possible successive layers.
Usually can in 10 to 15 minutes, obtain attractive and durable dental prosthesis.
Should be noted that the product right and wrong that obtained by dental composition of the present invention are porous.Therefore, for example after polishing through optional felt brush, the surface of the dental prosthesis that is obtained is smooth shinny, thereby does not need to use varnish.
In the dental prosthesis Application for Field mainly is the application of additional prosthese, can be divided into two classes:
-complete mouthful the prosthese that under the situation of the complete anodontia of patient, uses;
-owing to lack the part prosthese that several teeth use, it shows as temporarily with prosthese or frame prostheses.
In the dental prosthetic field, dental composition of the present invention can be used as the nipper of filling different colours (as " VITA " look) and the material of back tooth, and it is fast with wieldy.
Because this dental composition is nontoxic and can aggregates into thick layer, therefore there is no need with successive layers mode polymeric material.Usually this dental composition of a shot is enough.
The preparation of dental prosthesis and repair materials is carried out according to this area method commonly used.
Be applied at this dental composition under the situation of tooth, or utilize mordant to utilize the bonding priming paint of itself Photocrosslinkable that tooth is carried out pre-treatment then, or prepare dental composition by before using, mixing with bonding priming paint.
The invention still further relates to the method for handling reinforcing filler, particularly dental reinforcing filler is characterized in that this filler utilizes following mass treatment:
A) at least a organo-silicon coupling agent (F) and
B) at least a compound (G),
Described organo-silicon coupling agent (F) comprises that the active function groups (rfC) that directly is connected in active function groups (rfA) on the Siliciumatom and at least one and compound (G) of at least one and dental filler reaction reacts directly is not connected in active function groups (rfB) on the Siliciumatom.
An optimal way according to the inventive method:
-the active function groups (rfA) that directly is connected on the Siliciumatom of organo-silicon coupling agent (F) is an alkoxyl group, alkene oxygen base and/or hydroxy functional group;
-the active function groups (rfB) that directly is not connected on the Siliciumatom of organo-silicon coupling agent (F) is an oxyethane, trimethylene oxide, hydroxyl, acid, carboxylic acid anhydride or functionalized with glycols group; With
The active function groups (rfC) of-compound (G) is an oxyethane, trimethylene oxide, alkenyl ether or carbonate functionalities.
According to another embodiment, this filler is through using following mass treatment:
A) at least a organo-silicon coupling agent (F), it comprises at least one and directly is connected in alkoxyl group and/or hydroxy functional group and at least one oxyethane on the Siliciumatom, trimethylene oxide, hydroxyl and/or functionalized with glycols group; With
B) at least a compound (G), it comprises at least one oxyethane, trimethylene oxide, alkenyl ether and/or carbonate functionalities.
Method of the present invention is specially adapted to handle the dental filler.This method (I) may further comprise the steps:
A) dental filler (B) and at least a organo-silicon coupling agent (F) are mixed in solvent medium, this organo-silicon coupling agent (F) comprises at least one and directly is connected in alkoxyl group on the Siliciumatom and/or hydroxy functional group and at least one oxyethane, trimethylene oxide, hydroxyl and/or functionalized with glycols group
B) evaporation removes to desolvate and obtains middle dental filler (B-1),
C) heat-treat this centre dental filler (B-1), so that carry out linked reaction between middle dental filler (B-1) and the coupling agent (F), and dental filler (B-2) in the middle of obtaining thus,
D) in solvent medium middle dental filler (B-2) is mixed with at least a compound (G) subsequently, this compound (G) comprises at least one oxyethane, trimethylene oxide, and alkenyl ether and/or carbonate functionalities,
E) evaporation remove desolvate obtain in the middle of dental filler (B-3) and
F) heat-treat this centre dental filler (B-3), so that react between middle dental filler (B-3) and the compound (G), obtains treated dental filler (B-4) thus.
According to a kind of preferred mode, step c) and f in the method (I)) thermal treatment be less than or equal to 200 ℃ by being heated to, preferably be less than or equal to 160 ℃, more preferably 100 to 165 ℃ temperature is carried out.
Organo-silicon coupling agent (F), compound (G) and dental reinforcing filler (B) are by the definition in the dental composition of the present invention.
The present invention also relates to the reinforcing filler that obtains through the inventive method.
Embodiment
The following examples and test provide in illustrative mode.These embodiment and test especially make it possible to more to be expressly understood the present invention and outstanding its some advantages, and set forth its some embodiments.
Embodiment and test
Structure
The resin that-DOW CHEMICAL company sells with label ERLX-4360 (with a resinoid of said structure S-104 description),
-filler (B-1): silica glass (particle size=1.5 μ m, SiO that Schott company sells with label G018-163
256%; SrO 14%, B
2O
314%; Al
2O
314%; F 2%).
-filler (B-2): silica glass (particle size=1.5 μ m, SiO that Schott company sells with label GM27-884
255%; BaO 25%, B
2O
310%; Al
2O
310%).
The thioxanthone (S-61) of preparation boronic acid containing ammonium functionality:
Chlorination 3-(3,4-dimethyl-9-oxygen-9H-thioxanthene-2-base oxygen base)-2-hydroxypropyl at the 1.02g that in opaque bottle, packs under the no optical condition) trimethyl ammonium (sale of Aldrich company); " 2.688g kisbore " salt KB (C
6F
5)
4(sale of Rhodia company) and 50ml Virahol, and under magnetic agitation, placed 48 hours at ambient temperature.Mixture is injected in the softening water (200ml) subsequently.Form yellow mercury oxide.Suspension filters through B, and solid is at 100 ℃ of baking oven inner drying 24h.Obtain mentioned salt (PS-31) (235 ℃ of fusing points; Maximum absorption λ max=397.3nm).
Embodiment 1 (Comparative Examples): the processing of filler (B-1)
A) handle filler with the coupling agent (F-2) that contains the functionalized with glycols degree:
GLYMO shown in the formula (F-1) that silane glycidyl oxygen base propyl trimethoxy silicane or Degussa company sell in acidic medium according to following reaction hydrolysis:
R=methyl wherein
Compound (F-2) is the form of more or less polycondensation and in that to contain aqueous phase solvable.
The solution that uses is the solution that contains the pH=3-4 of 40% silane (F-2).
This 40% silane of 12.5g (F-2) solution is poured in the beaker and supplied with the 200g softening water.200g filler (B-1) is poured in this solution and mixture at room temperature stirred 1 hour with impeller-type stirrer.Mixture is poured in the crystallizing pan, and filler in baking oven 150 ℃ of dryings 16 hours.Filler is through 250 microns mesh screen branch then.
B) with the coupling agent treatment that contains the oxyethane functionality
In order to contrast, we carry out the hydrolysis of silane glycidyl oxygen base propyl trimethoxy silicane in neutral medium, and remove the most of methyl alcohol that is produced by hydrolysis reaction by distillation.
1H NMR analysis revealed, epoxy-functional does not have hydrolysis when the cold poke of this solution is all.
Use 40% silane (F-3) solution of pH=7.
This 40% solution of 12.5g is poured in the beaker and supplied with the 200g softening water.The untreated filler of 200g (B-1) is poured in this solution and mixture at room temperature stirred 1 hour with impeller-type stirrer.Mixture is poured in the crystallizing pan, and filler in baking oven 150 ℃ of dryings 16 hours.Filler is through 250 microns mesh screen branch then.
C) performance of dental composition
The silicone resin (S-1) that 11.625g is contained oxyethane functional group is put into centrifugal mixer (trade mark Hauschild).
(Byk company is with label to add 4% the dispersion agent (C-1) of 1.125g
Sell) solution.Mixture stirred 16 seconds with 3000rpm with centrifugal mixer, added 3g three then and fluoridized ytterbium.Mixture, adds 1.25g then and is dissolved in photoinitiator system (P) in (S-1) with 3000rpm restir 16 seconds with centrifugal mixer, and this system contains the photosensitizers of 30 weight % light triggers (P-22) and 0.89 weight % formula (PS-31).
Mixture at room temperature stirred 16 seconds with 3000rpm with centrifugal mixer, added 25g filler (B-1) then:
-be untreated (preparaton 1t),
-or according to a) handling (preparaton 1a);
-or according to b) processing (preparaton 1b).
Mixture stirred 16 seconds with centrifugal mixer.Add 3g combustion method silica-type filler (B-3) (SiO
2＞99%, Degussa company is with label
Sell), stirred the mixture then 16 seconds.At last, add 5g Degussa company with label
The combustion method silica-type filler of selling (B-4) stirred the mixture 16 seconds then.
Monitor three kinds of preparaton viscosity over time.The record synergistic formulation gelation and the no longer exercisable moment.The results are shown in Table 1.
Table 1
| Comparative Examples | Stability under 25 ℃ |
| Preparaton 1t | ＜24h |
| Preparaton 1a | ＜24h |
| Preparaton 1b | 48h |
Embodiment 2 (the present invention)
A) handle by embodiment 1a with the resin (S-1) that contains oxyethane functional group) filler that obtains
Preparation contains the solution that 2.5 weight % contain the resin (S-1) of oxyethane functional group in acetone.
100g is according to embodiment 1a) filler (B-1) handled pours in this 2.5% solution of 100g, and at room temperature mechanical stirring is about 1 minute.Then mixture is poured in the crystallizing pan, at room temperature evaporated acetone.
Resistates heats 16 hours so that contain the surface aggregate of the resin (S-1) of oxyethane functional group at filler at 150 ℃.Screen this filler then and obtain powder.
B) handle by embodiment 1b with the resin (S-1) that contains oxyethane functional group) filler that obtains
Preparation contains the solution that 2.5 weight % contain the resin (S-1) of oxyethane functional group in acetone.
100g is according to embodiment 1b) filler (B-1) handled pours in this 2.5% solution of 100g, and at room temperature mechanical stirring is about 1 minute.Then mixture is poured in the crystallizing pan, at room temperature evaporated acetone.Resistates heats 16 hours so that contain the surface aggregate of the resin (S-1) of oxyethane functional group at filler at 150 ℃.Screen this filler then and obtain powder.
C) performance of dental composition
Embodiment 2-a) and embodiment 2-b) two kinds of fillers according to embodiment 1-c) same way as preparation, overall filler content is 72 weight % with respect to the weight of composition, thereby obtain two kinds of dental compositions (be respectively preparaton (2a) and (3b)), monitor its in time stability and change.
Table 2
| The present invention | Handle | Stability under 25 ℃ |
| Preparaton (2a) | A) contain the solution of 2.5% weight resin (S-1) | 1 month |
| Preparaton (2b) | B) contain the solution of 2.5% weight resin (S-1) | 1 week |
By comparing:
-preparaton (1a) and (2a) between, and
-preparaton (1b) and (2b) between the result can see that stability obviously improves.
Embodiment 3 (the present invention, the dual processing of filler)
Contain the variation of content of the resin (S-1) of oxyethane functional group
Repeat embodiment 2a), change contains the content of the resin (S-1) of oxyethane functional group in filler (B-1) treating processes.
Then according to embodiment 2c) the preparation dental composition.
Concrete composition is corresponding to following prescription (overall filler content is 66 weight % with respect to composition weight):
-contain the resin (S-1) of oxyethane functional group----------〉29.25g
-contain the dispersant solution of 4% (C-1)---------2.25g
-photoinitiator system (P) (seeing embodiment 1):
(P-22)+(PS-31) ----------> 2.5g
-three fluoridize ytterbium----------〉6g
The filler of-dual processing (B-1)----------〉50g
-undressed filler (B-3)
Combustion method silicon-dioxide
----------〉5g
-undressed filler (B-4)
Combustion method silicon-dioxide
----------〉5g
Monitor the ring oxygen content change by the potentiometric analysis of this complex solution in the perchloric acid analytical solution.
Table 3
| Dental composition | Be used for handling the weight % of the resin (S-1) of filler (B-1) at acetone | Epoxy degree of conversion % after 26 days | 25 ℃ of stability (moon) |
| Control formulation (1t) | 0 | Can't detect | 0 |
| Preparaton (3a) | 1 | 23 | 1 |
| Preparaton (3b) | 2.5 | 19 | 3 |
| Preparaton (3c) | 5 | 16 | ＞December |
Embodiment 4 (the present invention, the dual processing of filler): preparation has 70 weights with respect to composition weight
The dental composition of amount % overall filler content.
The silicone resin (S-1) that 11.5g is contained oxyethane functional group is put into the Hauschild centrifugal mixer.Add 2.25g Byk company with label Disperbyk-
4% solution of the dispersion agent of selling (C-1).Mixture stirred 16 seconds with 3000rpm with centrifugal mixer, and adding 3g three fluoridizes ytterbium.Mixture stirred 16 seconds with 3000rpm with centrifugal mixer, added 1.25g then and was dissolved in photoinitiator system (P) in the resin (S-1), and this system contains 30 weight % light triggers (P-22) and the 0.89 weight % photosensitizers based on (PS-31).Mixture at room temperature stirred 16 seconds with 3000rpm with centrifugal mixer, added 27g then according to embodiment 2a) filler (B-1) handled according to embodiment 3 (handling filler (B-1)) then with the acetone soln that contains 5 weight % resins (S-1).Mixture stirred 16 seconds with centrifugal mixer.(Degussa company is with label according to combustion method silicon-dioxide (B-3) that filler (B-1) is handled to add 2.5g
Sell SiO
2＞99%), stirred the mixture then 16 seconds.At last, (Degussa company is with label to add 2.5g combustion method silicon-dioxide (B-4)
Sell), stirred the mixture then 16 seconds.
For the preparaton that contains treated filler, monitor its viscosity over time.This preparaton is can stably stored under 25 ℃ more than 1 year.
The sample that standard ISO 4049 is described is to use Demetron Optilux 500 type halogen lamps (radiated time: 2 times 40 seconds) to carry out crosslinked.
The flexural strength of measuring according to standard ISO-4049 is that 90MPa+/-10 and modulus in flexure are 9000MPa.
Radiation after 40 seconds crosslinked thickness be 4mm.
By before the polymerization and the volumetric shrinkage that draws of the density calculation of measurement after the polymerization be :-1.6%+/-0.2.
Concrete composition is corresponding to following prescription (overall filler content is 70 weight % with respect to composition weight):
-contain the resin (S-1) of oxyethane functional group----------〉11.5g
-dispersant solution (C-1)----------〉2.25g
-photoinitiator system (P):
(P-22)+(PS-31) ---------->1.25g
-treated three fluoridize ytterbium----------〉3g
The filler of-dual processing (B-1)----------〉27g
-undressed filler (B-3)
Combustion method silicon-dioxide
----------〉2.5g
-undressed filler (B-4)
Combustion method silicon-dioxide
----------〉2.5g
Embodiment 5 (the present invention, the dual processing of filler)
Relatively the kind of photosensitizers is to through the painted influence of composition after the radiation of dental lamp.Repeat embodiment 4, change the kind and the quantity that are incorporated into the photosensitizers in the composition.
Dental composition described in the embodiment 2 to 5 is 2 to 3mm with the crosslinked thickness of Optilux Demetron lamp 30 seconds to 1 minute time of radiation.On white background, measuring after crosslinked 15 minutes and after crosslinked 5 days, measuring L*, a* and b* value by means of Minolta CR200 chromascope or colorimeter.
The gamut Δ c that derives thus and produced: Δ c=[(Δ a)
2+ (Δ b)
2]
1/2
Can observe, by means of Demetron Optilux 500 dental lamps, utilize use separately or with other photosensitizers as (PS-39), (PS-34) and the crosslinked painted defective (do not occur pink phenomenon in the radiative process, promptly have colourimetric number a＞1 after the radiation) that do not produce of the dental composition prepared of the photosensitizers that (PS-33) is used in combination (PS-31).
Table 4
Coloring problem can be eliminated by the combination of using thioxanthone (PS-31), and the dynamics problem that independent use camphorquinone (PS-34) or camphorquinone are run into when using in conjunction with lower concentration anthracene derivant (PS-39) (in embodiment 5-h less than 0.1%) can be eliminated.
Embodiment 6:(the present invention, the dual processing of filler)
Repeat embodiment 5:
-replace light trigger (P-22) with light trigger (P-29); With
-replace photoinitiator system (P) with photoinitiator system (P '), this photoinitiator system (P ') is included in 30 weight % light triggers (P-29) in the resin (S-1) and the 0.89 weight % photosensitizers based on (PS-31).
Gamut:
After-crosslinked 15 minutes, on white background, L*, a*, b* is respectively 72.1; + 0.10; 9.53; With
After-5 days, L*, a*, b* is respectively 75;-0.25; 8.1;
＝＞Δc＝[(Δa)
2+(Δb)
2]
1/2＝1.47。
Embodiment 7:(the present invention, the dual processing of filler)
A) handle filler (B-2) with glycidyl oxygen base propyl trimethoxy silicane
The acetone soln that 300g is contained 2.5% glycidyl oxygen base propyl trimethoxy silicane is joining under the condition of nitrogen gas on the 300g glass B-2.The impeller that applies with Teflon of mixture vigorous stirring 8 hours at room temperature then.Filter then in " slurry ", with recovery glass, and filter cake is by 200 microns mesh screens choosings.The glass of screening was 110 ℃ of following dry airs 8 hours.
B) with containing the resin (S-1) of oxyethane functionality and mixture process (S-104) by embodiment 7-a) filler (B-2) that obtains.
The acetone soln that 300g is contained 3.8% (S-1) and 3.8% (S-104) joins 300g according to embodiment 7-a) handle on glass, mixture at room temperature stirred 8 hours with the impeller that Teflon applies under condition of nitrogen gas then.
Glass filters through the polymeric amide strainer, then by 200 microns mesh screens choosings, at last 110 ℃ dry 12 hours down.
Resulting treated glass (filler of dual processing) is used to prepare following dental composition (overall filler content is 75% with respect to the gross weight of composition) then:
-contain the resin (S-1) of oxyethane functional group----------〉4.5g
-contain resin (S-104)---------4.5g of oxyethane functionality
-dispersant solution (C-1)----------〉2.25g
-photoinitiator system (P): (P22)+(PS-31)----------〉1.25g
The filler of-dual processing (B-2)----------〉32.5g
The filler of-dual processing (B-3)
Combustion method silicon-dioxide
----------〉2.5g
-undressed filler (B-4)
Combustion method silicon-dioxide
----------〉2.5g
The epoxy content of monitoring composition over time.Observe composition 25 ℃ can stably stored at least 9 months, the transforming degree of epoxy is less than 20%.
Standard ISO 4049 described samples are to use Demetron Optilux 500 type halogen lamps (radiated time: 2 times 40 seconds) to carry out crosslinked.
The flexural strength of measuring according to standard I S0-4049 is that 90MPa+/-10 and modulus in flexure are 8000MPa+/-1000.
Radiation after 40 seconds crosslinked thickness be 4mm.
By before the polymerization and the volumetric shrinkage that draws of the density calculation of measurement after the polymerization be :-1.4%+/-0.2.
Embodiment 8 (the present invention, the dual processing of filler)
According to embodiment 7b) the treated glass (filler of dual processing) that obtains is used to prepare following dental composition (overall filler content is 75% with respect to composition total weight) then:
-contain the resin (S-1) of oxyethane functional group----------〉4.5g
-contain resin (S-104)---------4.5g of oxyethane functionality
-dispersant solution (C-1)----------〉2.25g
-photoinitiator system (P): (P22)+(PS-31)----------〉1.25g
The filler of-dual processing (B-2)----------〉32.5g
The filler of-dual processing (B-3)
Combustion method silicon-dioxide
----------〉2.5g
-undressed filler (B-5)
Colloidal silica is approximately 40 as concentration
The solution of the resin of weight % (S-96),
Sell by Hanse Chemie company----------〉2.5g
The epoxy content of monitoring composition over time.Observe composition and can stablize at least 9 months at 25 ℃, the transforming degree of epoxy is less than 20%.
Standard ISO 4049 described samples are to use Demetron Optilux 500 type halogen lamps (radiated time: 2 times 40 seconds) to carry out crosslinked.
The flexural strength of measuring according to standard ISO-4049 is that 100MPa+/-10 and modulus in flexure are 8000MPa+/-1000.
Radiation after 40 seconds crosslinked thickness be 4mm.
By before the polymerization and the volumetric shrinkage that draws of the density calculation of measurement after the polymerization be :-1.4%+/-0.2.
Claims (37)
1. dental composition, said composition comprises:
(1) at least a by the reactive compound of positively charged ion approach (A);
(2) at least a dental filler (B);
(3) randomly, at least a dispersion agent (C), it comprises at least a organic polymer;
(4) at least a cation light initiator (D);
(5) and randomly, at least a photosensitizers (E), described composition are characterised in that said composition comprises at least a dental filler (B), and this dental filler (B) has passed through the processing of the method (I) that comprises the following steps:
A) with dental filler (B) and at least a organo-silicon coupling agent (F) with following structural
In solvent medium, mix:
Wherein:
-R is the C1-C4 alkyl of hydrogen atom or linearity or branching,
-R
1Be the alkyl or the phenyl of linearity or branching,
-x is 0,1 or 2, and
X is defined by following structural:
Wherein:
-E and D are identical or different groups, are selected from the C1-C12 alkyl of linearity or branching,
-z is 0 or 1,
-n is 0 or 1,
-p is 0,1,2,3,4,5 or 6;
-R
2, R
3, R
4, R
5, R
6, R
7And R
8Be identical or different group, the C1-C12 alkyl of expression hydrogen or linearity or branching,
B) evaporation removes to desolvate and obtains middle dental filler (B-1),
C) heat-treat this centre dental filler (B-1), so that carry out linked reaction between middle dental filler (B-1) and the coupling agent (F), and dental filler (B-2) in the middle of obtaining thus,
D) then in solvent medium, middle dental filler (B-2) is mixed with at least a compound (G), this compound (G) is to comprise at least one oxyethane, trimethylene oxide, the organic or organo-siloxane monomer of alkenyl ether and/or carbonate functionalities, oligopolymer or polymkeric substance
E) evaporation remove desolvate obtain in the middle of dental filler (B-3) and
F) heat-treat this centre dental filler (B-3), so that react between middle dental filler (B-3) and the compound (G), obtains treated dental filler (B-4) thus.
2. the dental composition of claim 1, wherein step c) and the f in the method (I)) thermal treatment undertaken by being heated to the temperature that is less than or equal to 200 ℃.
3. claim 1 or 2 dental composition, wherein with respect to the gross weight of dental composition, the total content of dental filler (B) is up to 85 weight %.
4. claim 1 or 2 dental composition, wherein to be to use with respect to the dental composition gross weight be to carry out compound (G) that is up to 20 weight % and/or the organo-silicon coupling agent (F) that is up to 20 weight % in the processing of dental filler (B).
5. claim 1 or 2 dental composition, wherein organo-silicon coupling agent (F) is selected from following compounds: glycidyl oxygen base propyl trimethoxy silicane, the hydrolysate of glycidyl oxygen base propyl trimethoxy silicane; Glycidyl oxygen base propyl-triethoxysilicane, the hydrolysate of glycidyl oxygen base propyl-triethoxysilicane in acidic medium; Glycidyl oxygen base propyl group dimethoxy-methyl silane or its hydrolysate, β-(3,4-epoxy group(ing) cyclohexyl) ethyl triethoxysilane or its hydrolysate, β-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane or its hydrolysate.
6. claim 1 or 2 dental composition, wherein compound (G) comprises at least one and is selected from following (M-7) functional group to structure shown in (M-12):
(M-11)-(CH
2)
3-O-CH＝CH
2；
(M-12)-(CH
2)
3-O-CH＝CH-R″
" the C of expression linearity or branching of R wherein
1-C
6Alkyl group.
7. the dental composition of claim 1, wherein compound (G) is organosilicon oligopolymer (G-1) or organosilicon polymer (G-2).
8. the dental composition of claim 7, wherein organosilicon oligopolymer (G-1) or organosilicon polymer (G-2) comprise:
A) at least a unit of following formula:
Wherein:
-a=0,1 or 2,
-R
0, identical or different, the expression alkyl, cycloalkyl, aryl, vinyl, hydrogen or alkoxy base,
-Z, identical or different, the expression contain at least one oxyethane, alkenyl ether, the organic substituent of trimethylene oxide and/or carbonate functionalities and
B) at least two Siliciumatoms.
9. the dental composition of claim 8, wherein organosilicon oligopolymer (G-1) or organosilicon polymer (G-2) are selected from the compound shown in the following structural:
L=H; OH; Me; Phenyl; The C1-C12 alkyl; C1-C6 cycloalkyl or following radicals:
N＜100 wherein; A＜100 and m＜100,
N＜100 wherein
(S-15)
In these structural formulas, R
0Be identical or different, expression alkyl, cycloalkyl or aromatic yl group.
10. claim 1 or 2 dental composition wherein are selected from by the reactive compound of positively charged ion approach (A) and comprise Resins, epoxy, vinyl ether, trimethylene oxide, spiro original magnesium ester, the monomer and/or the polymkeric substance of spiral shell original carboxylic acid ester and their combination.
11. the dental composition of claim 10, wherein form by at least a crosslinkable and/or polymerisable organosilicon oligopolymer (G-1) or organosilicon polymer (G-2) by the reactive compound of positively charged ion approach (A), this organosilicon oligopolymer (G-1) or organosilicon polymer (G-2) but at room temperature be in a liquid state or be hot melt being lower than under 100 ℃ the temperature, and comprise:
A) at least a unit of following formula:
Wherein:
-a=0,1 or 2,
-R
0, identical or different, the expression alkyl, cycloalkyl, aryl, vinyl, hydrogen or alkoxy base,
-Z, identical or different, the expression contain at least one oxyethane, alkenyl ether, trimethylene oxide, the organic substituent of dioxolane and/or carbonate functionalities and
B) at least two Siliciumatoms.
12. the dental composition of claim 11 is characterized in that (M-13) unit comprises to be selected from following (R-1) group Z to (R-9) group:
(R-8)-(CH
2)
3-O-CH＝CH
2；
(R-9)-(CH
2)
3-O-CH＝CH-R″
-R wherein " the C1-C6 alkyl group of expression linearity or branching.
13. the dental composition of claim 1 or 2 is characterized in that being selected from the compound described in the claim 9 (S-1) to (S-15) by the reactive compound of positively charged ion approach (A).
14. the dental composition of claim 1 or 2, it is characterized in that cation light initiator (D) be the borate type and be selected from such material, for this material:
A) boratory cationic moiety is selected from:
(1) salt of following formula:
[(R
9)
n-A-(R
10)
m]
+ (I)
Wherein:
-A represents 15 to 17 family's elements,
-R
9Expression C6-C20 heterocycle or carbon ring aromatic yl group, described heterocyclic group randomly comprise nitrogen or the assorted element of sulphur conduct,
-R
10Expression R
9Or the alkyl of C1-C30 linearity or branching or kiki alkenyl group; Described radicals R
9And R
10Randomly by the C1-C25 alkoxyl group, the C1-C25 alkyl, nitro, chlorine, bromine, cyano group, carboxyl, ester group or sulfydryl replace,
-m and n are integers, n+m=v+1 wherein, and v is the valency of elements A,
(2) oxo different sulfo-chroman salt and
(3) organic metal salt as follows:
(L
1L
2L
3M)
+q (II)
Wherein:
-M represents 4 to 10 family's metals,
-L
1Expression is by 1 part of πDian Zi and metal M keyed jointing, and this part is selected from η
3-alkyl, η
5-cyclopentadienyl and η
7-cycloheptatriene ylidene ligands and η
6-aromatics, this compound are selected from the optional η that replaces
6-benzene part and compound with 2 to 4 condensed ring, each ring can be contributed the valence shell of metal M by 3 to 8 πDian Zis,
-L
2Expression is by the part of πDian Zi and metal M keyed jointing, and this part is selected from η
7-cycloheptatriene ylidene ligands and η
6-aromatics, this compound are selected from the optional η that replaces
6-benzene part and compound with 2 to 4 condensed ring, each ring can be contributed the valence shell of metal M by 6 or 7 πDian Zis,
-L
3Expression is by 0-3 identical or different part of σDian Zi and metal M keyed jointing, and this part is selected from CO and NO
2 +, L
1, L
2And L
3With the ionic charge contribution of metal M to total elementary charge q of title complex for just and be 1 or 2; With
B) borate anion partly has structural formula:
[BX
aR
b]
- (III)
Wherein:
-a is 0 to 3 integer, and b is 1 to 4 integer, a+b=4 wherein,
-symbol X represents:
* halogen atom, a=0 to 3 wherein, perhaps
* OH functional group, a=0 to 2 wherein,
-symbol R is identical or different, and:
-when cationic moiety was the positively charged ion of 15 to 17 family's elements, R represented by at least a electron-withdrawing group and/or the phenyl that replaced by at least two halogen atoms,
-when cationic moiety was the organometallic complex of 4 to 10 family's elements, R represented the phenyl that replaced by at least a electrophilic element or group, or
-no matter be any cationic moiety, R represents to comprise the aryl of at least two virtue nuclears, and it is optional by at least a electrophilic element or group replacement.
15. the dental composition of claim 14 is characterized in that cation light initiator (D) is selected from following compounds:
(P-16)：[(C
8H
17)-O-C
6H
4-I-C
6H
5)]
+，[B(C
6F
5)
4]
-；
(P-17)：[C
12H
25-C
6H
4-I-C
6H
5]
+，[B(C
6F
5)
4]
-；
(P-18)：[(C
8H
17-O-C
6H
4)
2I]
+，[B(C
6F
5)
4]
-；
(P-19)：[(C
8H
17)-O-C
6H
4-I-C
6H
5)]
+，[B(C
6F
5)
4]
-；
(P-20)：[(C
6H
5)
2S-C
6H
4-O-C
8H
17]
+，[B(C
6H
4CF
3)
4]
-；
(P-21)：[(C
12H
25-C
6H
4)
2I]
+，[B(C
6F
5)
4]
-；
(P-22)：[CH
3-C
6H
4-I-C
6H
4-CH(CH
3)
2]
+，[B(C
6F
5)
4]
-；
(P-23): (η
5-cyclopentadienyl) (η
6-toluene) Fe
+, [B (C
6F
5)
4]
-
(P-24): (η
5-cyclopentadienyl) (η
6-1-methylnaphthalene) Fe
+, [B (C
6F
5)
4]
-
(P-25): (η
5-cyclopentadienyl) (η
6-isopropyl benzene) Fe
+, [B (C
6F
5)
4]
-
(P-26)：[C
12H
25-C
6H
4)
2I]，[B(C
6H
3(CF
3)
2]
-；
(P-27)：[CH
3-C
6H
4-I-C
6H
4-CH
2CH(CH
3)
2]
+，[B(C
6F
5)
4]
-；
(P-28): [CH
3-C
6H
4-I-C
6H
4-CH
2CH (CH
3)
2]
+, [B (C
6H
3(CF
3)
2)
4]
-With
(P-29)：[CH
3-C
6H
4-I-C
6H
4-CH(CH
3)
2]
+，[B(C
6H
3(CF
3)
2)
4]
-。
16. the dental composition of claim 1 is characterized in that cation light initiator (D) is a salt compounded of iodine.
17. the dental composition of claim 1 or 2, wherein photosensitizers (E) comprises one or more replacements or unsubstituted virtue nuclear in its structure, and it has 200 to 500nm residual light absorption.
18. the dental composition of claim 1 or 2, wherein photosensitizers (E) is selected from anthracene, thioxanthone, the compound of camphorquinone and phenanthrenequione class and their mixture.
19. the dental composition of claim 18, wherein photosensitizers (E) is by at least a thioxanthone salt that contains the group replacement of ammonium functional group.
20. the dental composition of claim 19 is characterized in that the association negatively charged ion of the thioxanthone salt that replaced by at least a group that contains ammonium functional group is selected from following negatively charged ion: halogen root, BF
4 -, PF
6 -SbF
6 -Formula [the BX of claim 14 definition
aR
b]
-Negatively charged ion (III), R
fSO
3 -(R
fSO
2)
3C
-Or (R
fSO
2)
2N
-, R wherein
fBe the alkyl of linearity or branching, it is replaced by at least one halogen atom.
21. the dental composition of claim 1 or 2, wherein randomly with at least a camphorquinone, the anthracene bonded photosensitizers (E) of phenanthrenequione and/or replacement has following structural:
Wherein:
-R
22And R
23Be identical or different, expression hydrogen or the optional C1-C10 alkyl that replaces,
-(Y) be anionic species.
22. the dental composition of claim 1 or 2, wherein randomly with at least a camphorquinone, the anthracene bonded photosensitizers (E) of phenanthrenequione and/or replacement has following structural:
23. the dental composition of claim 1 or 2, wherein photosensitizers (E) is selected from following compounds:
-(PS-30): trimethyl ammonium chlorination 3-(3,4-dimethyl-9-oxo-9-thioxanthene-2-base-oxygen base)-2-hydroxypropyl);
-(PS-31): trimethyl ammonium four (pentafluorophenyl group) boric acid 3-(3,4-dimethyl-9-oxo-9-thioxanthene-2-base-oxygen base)-2-hydroxypropyl);
-(PS-32): trimethyl ammonium four (two (trifluoromethyl) phenyl) boric acid 3-(3,4-dimethyl-9-oxo-9-thioxanthene-2-base-oxygen base)-2-hydroxypropyl);
-(PS-33): phenanthrenequione;
-(PS-34): camphorquinone;
-(PS-35): acenaphthenequinone;
-(PS-36): dibenzoyl peroxide;
-(PS-37): 2-ethyl-9,10-dimethoxy anthracene;
-(PS-38): 9,10-diethoxy anthracene;
-(PS-39): 9,10-dibutoxy anthracene;
-(PS-40): 9-methylol anthracene;
-(PS-41): 2-dimethylamino thioxanthone;
-(PS-42): 3-ethyl carboxyl-7-methoxyl group thioxanthone;
-(PS-43): 1-phenyl sulfo--4-propoxy-thioxanthone;
-(PS-44): 2-methoxyl group thioxanthone;
-(PS-45): 2-(N, N-diethylamino propoxy-) thioxanthone;
-(PS-46): the 2-isopropyl thioxanthone;
-(PS-47): 1-chloro-4-propoxy-thioxanthone;
-(PS-48): the 4-isopropyl thioxanthone;
-and the mixture of above-mentioned substance.
24. the dental composition of claim 1 or 2, wherein photosensitizers (E) is selected from tonka bean camphor, diketone, fluorone, keto-amine and the compound of right-amino-benzene vinyl ketones and their mixture.
25. each dental composition of claim 7-9, wherein organosilicon polymer (G-2) or organosilicon oligopolymer (G-1) are with formula (S-103) or the organic Resins, epoxy resin-bonded (S-104):
Wherein:
-0≤n≤100 and
-D=is selected from the group of the C1-C12 alkyl of linearity or branching.
26. the dental composition of claim 1 or 2, wherein dental filler (B) is unorganic glass or combustion method silicon-dioxide.
27. the dental composition of claim 1 or 2, wherein compound (G) is selected from following molecule:
28. the dental composition of claim 1 or 2, wherein compound (G) is the organic compound (G-4) that is selected from molecule (S-96) to (S-104):
In these structural formulas: n is the integer between 1 to 10, comprises end value interior,
The C1-C12 alkyl of n＜100 and D=linearity or branching wherein,
The C1-C12 alkyl of n＜100 and group D=linearity or branching wherein.
29. be used to handle the method (I) of dental reinforcing filler, this method comprises the following steps:
A) dental reinforcing filler (B) and at least a organo-silicon coupling agent (F) with following structural are mixed in solvent medium:
Wherein:
-R is the C1-C4 alkyl of hydrogen atom or linearity or branching,
-R
1Be the alkyl or the phenyl of linearity or branching,
-x is 0,1 or 2, and
X is defined by following structural:
Wherein:
-E and D are identical or different groups, are selected from the C1-C12 alkyl of linearity or branching,
-z is 0 or 1,
-n is 0 or 1,
-p is 0,1,2,3,4,5 or 6;
-R
2, R
3, R
4, R
5, R
6, R
7And R
8Be identical or different group, the C1-C12 alkyl of expression hydrogen or linearity or branching,
B) evaporation removes to desolvate and obtains middle dental filler (B-1),
C) heat-treat this centre dental filler (B-1), so that carry out linked reaction between middle dental filler (B-1) and the coupling agent (F), and dental filler (B-2) in the middle of obtaining thus,
D) then in solvent medium, middle dental filler (B-2) is mixed with at least a compound (G), this compound (G) is to comprise at least one oxyethane, trimethylene oxide, the organic or organo-siloxane monomer of alkenyl ether and/or carbonate functionalities, oligopolymer or polymkeric substance
E) evaporation remove desolvate obtain in the middle of dental filler (B-3) and
F) heat-treat this centre dental filler (B-3), so that react between middle dental filler (B-3) and the compound (G), obtains treated dental filler (B-4) thus.
30. the method that is used to handle the dental reinforcing filler of claim 29, wherein step c) and the f in the method (I)) thermal treatment undertaken by being heated to the temperature that is less than or equal to 200 ℃.
31. each the method that is used to handle the dental reinforcing filler in the claim 29 to 30, wherein organo-silicon coupling agent (F) is according to definition in the claim 5.
32. each the method that is used to handle the dental reinforcing filler in the claim 29 to 30, wherein compound (G) is according to defining in each in the claim 6 to 8.
33. each the method that is used to handle the dental reinforcing filler in the claim 29 to 30, wherein reinforcing filler is unorganic glass or combustion method silicon-dioxide.
34. the reinforcing filler that obtains by each method in the claim 29 to 33.
35. each dental composition is used to prepare dental prosthesis or is used to prepare the purposes of dental prosthetic with material among the claim 1-28.
36. dental prosthesis by each composition acquisition in the crosslinked claim 1 to 28.
37. dental prosthetic material by each composition acquisition in the crosslinked claim 1 to 28.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0405177 | 2004-05-13 | ||
| FR0405177 | 2004-05-13 | ||
| FR0407209 | 2004-06-30 |
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| US8883710B2 (en) | 2008-05-16 | 2014-11-11 | The Procter & Gamble Company | Compositions and methods incorporating photocatalysts |
| EP2424947A1 (en) * | 2009-05-01 | 2012-03-07 | The Procter & Gamble Company | Compositions and methods incorporating photocatalysts |
| JP2013510864A (en) * | 2009-11-13 | 2013-03-28 | ザ プロクター アンド ギャンブル カンパニー | Photocatalyst introduction composition and photocatalyst introduction method |
| JP6397823B2 (en) * | 2013-09-20 | 2018-09-26 | 信越化学工業株式会社 | Silicone-modified epoxy resin and composition and cured product thereof |
| BR112016007704B1 (en) * | 2013-10-07 | 2022-06-21 | Ppg Industries Ohio, Inc | Process for producing treated precipitated silica and rubber compounding |
| CN105837458B (en) * | 2016-04-07 | 2017-09-12 | 辽宁大学 | A kind of fluorescence probe and preparation method thereof and the application in detection peroxy acid |
| JP6737896B2 (en) * | 2016-04-27 | 2020-08-12 | ダウ シリコーンズ コーポレーション | Hydrophilic silane |
| CN107090179A (en) * | 2017-04-28 | 2017-08-25 | 东莞市俊怡化工科技有限公司 | A kind of multifunctional oral cavity composite and preparation method thereof |
| CN111454689B (en) * | 2019-12-31 | 2021-10-15 | 武汉长盈鑫科技有限公司 | Heat-conducting adhesive with high glass transition temperature and preparation method thereof |
| CN113980245B (en) * | 2021-12-01 | 2023-12-29 | 福建蓝海黑石新材料科技有限公司 | Lemon alkenyl silicon-containing cycloaliphatic epoxy resin and preparation and application methods thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321176A (en) * | 1998-10-07 | 2001-11-07 | 美国3M公司 | Radiopaque cationically polymerizable compositions comprising radiopacifying filler, and method for polymerizing same |
| US6362251B1 (en) * | 1998-10-09 | 2002-03-26 | Degussa-Huls Aktiengesellschaft | Dental material comprising porous glass ceramics, porous glass ceramics, processes and use |
-
2005
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321176A (en) * | 1998-10-07 | 2001-11-07 | 美国3M公司 | Radiopaque cationically polymerizable compositions comprising radiopacifying filler, and method for polymerizing same |
| US6362251B1 (en) * | 1998-10-09 | 2002-03-26 | Degussa-Huls Aktiengesellschaft | Dental material comprising porous glass ceramics, porous glass ceramics, processes and use |
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