U.S. patent application number 15/314198 was filed with the patent office on 2018-04-26 for reactive micro applicator with metal-containing additives for use in dental adhesives.
This patent application is currently assigned to HERAEUS KULZER GMBH. The applicant listed for this patent is HERAEUS KULZER GMBH. Invention is credited to Regina EPPINGER, Marcus HOFFMANN, Astrit KASTRATI, Waltraut LOH, Barbel QUINQUE.
Application Number | 20180110585 15/314198 |
Document ID | / |
Family ID | 53268807 |
Filed Date | 2018-04-26 |
United States Patent
Application |
20180110585 |
Kind Code |
A9 |
LOH; Waltraut ; et
al. |
April 26, 2018 |
REACTIVE MICRO APPLICATOR WITH METAL-CONTAINING ADDITIVES FOR USE
IN DENTAL ADHESIVES
Abstract
The invention relates to dental micro-applicators having a body
with a distal and a proximal end, whereby, on the proximal end, an
application aid is provided, at least in part, with at least one
additive selected from metals, metal-containing compounds, and
organometallic compounds for affecting the polymerisation of dental
materials, as well as a method for the production thereof and a kit
comprising the applicator and a dental adhesive.
Inventors: |
LOH; Waltraut; (Frankfurt,
DE) ; KASTRATI; Astrit; (Wollstadt, DE) ;
QUINQUE; Barbel; (Friedberg-Ockstadt, DE) ; EPPINGER;
Regina; (Weilburg, DE) ; HOFFMANN; Marcus;
(Usingen, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
HERAEUS KULZER GMBH |
Hanau |
|
DE |
|
|
Assignee: |
HERAEUS KULZER GMBH
Hanau
DE
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 20170189138 A1 |
July 6, 2017 |
|
|
Family ID: |
53268807 |
Appl. No.: |
15/314198 |
Filed: |
May 27, 2015 |
PCT Filed: |
May 27, 2015 |
PCT NO: |
PCT/EP2015/061692 PCKC 00 |
371 Date: |
November 28, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A46B 2200/202 20130101;
A46D 1/0207 20130101; A61C 3/005 20130101; A46B 2200/1066 20130101;
A61C 5/62 20170201; A61C 19/005 20130101; A46D 3/00 20130101; A46B
11/0072 20130101; A46B 15/0016 20130101; A61K 6/30 20200101; C08L
33/08 20130101; A61K 6/30 20200101; C08L 33/08 20130101 |
International
Class: |
A61C 3/00 20060101
A61C003/00; A61C 19/00 20060101 A61C019/00; A61C 5/62 20060101
A61C005/62; A46B 11/00 20060101 A46B011/00; A46D 3/00 20060101
A46D003/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 28, 2014 |
DE |
10 2014 107 518.8 |
Claims
1. Dental micro-applicator comprising (a) a body with a distal and
a proximal end and (b) an application aid on the proximal end,
wherein the application aid comprises, at least in part, at least
one additive selected from the group consisting of metals,
metal-containing compounds, and organometallic compounds for
affecting the polymerisation of dental materials.
2. Applicator according to claim 1, wherein the at least one
additive is present in nano-particulate form, optionally having a
particle size of less than or equal to 500 nm to more than or equal
to 1 nm.
3. Applicator according to claim 1, wherein the body consists of an
inert polymer selected from thermoplastic polymers comprising PE,
PP, HDPE, LDPE, porous expanded polypropylene (PEPP) and/or
expanded polypropylene (EPP).
4. Applicator according to claim 1, wherein the application aid on
the proximal end of the body comprises at least one a) filament,
brush, sponge, flakes, comb, ball, paintbrush, spatula, mixing pad
and/or porous means.
5. Applicator according to claim 1, wherein the application aid is
provided with at least one catalytically active metal or at least
one catalytically active organometallic compound.
6. Applicator according to claim 1, wherein the application aid is
provided with at least one catalytically active metal or at least
one catalytically active organometallic compound, whereby the metal
is selected from iron, cobalt, nickel, ruthenium, rhodium,
palladium, osmium, iridium, platinum, silver and copper, tin and
zinc.
7. Applicator according to claim 1, wherein the application aid is
impregnated, at least in part, with nano- particulate platinum.
8. Applicator according to claim 1, wherein the nano-particulate
platinum has a particle size of less than or equal to 10 nm, in
particular the nano-particulate platinum is platinum sponge.
9. Applicator according to claim 1, wherein the applicator
additionally comprises an excipient, activator and/or at least one
further additive, whereby the excipients comprise carboxylic acid,
salt of a carboxylic acid, buffer, hygroscopic compounds and/or the
at least one further additive is selected from base and
bases-releasing compounds.
10. Applicator according to claim 1, wherein the at least one
additive comprises at least one metal-containing compound that is
selected from alkaline salts, alkaline earth salts, inorganic salts
of alkali metals, inorganic salts of alkaline earth metals, alkali
metal hydroxides, alkaline earth metal hydroxides, organic alkaline
salts, organic alkaline earth salts, basic metal oxides,
base-forming agents, and metal-containing buffers.
11. Applicator according to claim 1, wherein the at least one
additive is at least one metal-containing compound selected from
alkali metal hydroxides, alkaline earth metal hydroxides, alkaline
earth oxides, and salts of carboxylic acids.
12. Method for producing a dental micro-applicator, comprising: (i)
providing a dental micro-applicator having a body with a distal and
a proximal end with an application aid on the proximal end; and
(ii) contacting the application aid contacted with at least one
additive selected from metals, metal-containing compounds, and
organometallic compounds for affecting the polymerisation of dental
materials.
13. Method according to claim 12, which further comprises: (Ii)
providing the at least one additive in a suspension, dispersion,
paste, solution or in the form of a powder.
14. Method according to claim 12, wherein (ii) the application aid
is contacted to a nano-particulate additive.
15. Method according to claim 11, wherein the nano-particulate
additive is at least one metal selected from catalytically active
metals and a metal compound showing an alkaline reaction.
16. Method according to claim 11, wherein the metal is
platinum.
17. Method according to claim 11, wherein the metal is present in a
suspension and said suspension comprises, in addition, an
excipient, an activator and/or a further additive, whereby the
excipient comprises at least one carboxylic acid, salt of a
carboxylic acid, buffer and/or base.
18. Method according to claim 11, wherein the content of the metal
in the suspension based on the total composition of the suspension
is 1.0 to 1.010-8% by weight.
19. Kit comprising a) an applicator according to claim 1, and b) a
dental adhesive.
20. Kit according to claim 18, wherein a) the applicator comprises
platinum as additive.
21. Kit according to claim 19, wherein the dental adhesive
comprises A) a radically polymerisable monomer having an acid group
in the molecule, B1) optionally, a photo-sensitiser and/or,
optionally, B2) a peroxide, C) a water-miscible solvent, and D)
water.
22. Kit according to cliam 19, which further comprises E) at least
one radically polymerisable monomer without an acid group.
23. Kit according to claim 19, which contains at least the one
additive selected from metal-containing compounds, in particular
alkali hydroxide, alkaline earth hydroxide, aluminium hydroxide,
zinc oxide, and organometallic compounds, alkaline salts or
alkaline earth salts of organic compounds.
24. Method of affecting the polymerisation of a dental material,
the method comprising providing at least one additive selected from
metals, metal-containing compounds, and organometallic compounds at
or on an application aid by contacting the at least one additive to
a polymerisable dental adhesive.
25. Method according to claim 24, wherein the polymerisable dental
adhesive is applied to a dental surface by means of the application
aid.
Description
[0001] The invention relates to a dental micro-applicator having a
body, whereby the body comprises a distal and a proximal end, and,
on the proximal end, an application aid is provided, at least in
part, with at least one additive selected from metals,
metal-containing compounds, and organometallic compounds for
affecting the polymerisation of dental materials, as well as a
method for the production thereof and a kit comprising the
applicator and a dental adhesive.
[0002] Numerous bondings and primer combinations are known for
improvement of the adhesion of dental materials to teeth. The
adhesives of recent generation comprise one-component self-etching
adhesives. To provide for good adhesion to the teeth, a large
adhesion surface that wets well must be provided. The adhesive
itself must be quite runny, comprise good wetting properties and
cure very rapidly in order to minimise any potential contact with
moisture and ensuing reduced adhesion.
[0003] Accordingly, self-etching adhesives are known that combine
the steps of acid etching and subsequent application of the
adhesive into one step. The acid-containing adhesive system
dissolves the smear layer and exposes the underlying dentine or
dissolves the smear layer only partially to make it permeable for
ingredients of the adhesive. The infiltration of the monomers into
the hard substance of the tooth takes place simultaneously. In case
of enamel, the acid-containing adhesive systems generate an etching
pattern that resembles phosphoric acid etching. The solvent
required for infiltration is removed with an air blower and the
adhesive is cured and/or radiation-cured.
[0004] It was the object of the invention to improve and/or
accelerate the curing of polymerisable dental materials. Moreover,
the shear bond strength of the dental materials was to be improved
further. It was another object of the invention to provide an aid
and a kit by means of which the polymerisation and, preferably by
this means, the curing and preferably the adhesion of dental
materials to dentine and/or to enamel can be improved. It was
another object to provide that, preferably, no further working
steps at user premises are required to accelerate the
polymerisation and, preferably, the curing, and preferably to
improve the adhesion to the tooth. Moreover, the treatment time was
to be shortened advantageously.
[0005] The objects are met by a dental micro-applicator according
to claim 1, by the method according to claim 11 for production of
the applicator as well as by the kit according to claim 19
comprising the applicator as well as by the inventive use according
to claim 24. Preferred embodiments are described in the sub-claims
and illustrated, in detail, in the description.
[0006] The objects of the invention are met by a micro-applicator
that is provided with at least one additive, which preferably
comprises catalytically active platinum, the applicator preferably
comprises platinum sponge as well as, optionally, at least one
further additive as well as, optionally, at least one excipient.
Alkaline additives capable of increasing the pH value of the
self-etching adhesive after the etching step in delayed manner have
proven valuable as further additive. For example disintegrants
(disintegration agents) or film-forming agents such as cellulose,
micro-crystalline cellulose, can be used as excipients.
[0007] The object of the invention is a dental micro-applicator
having a body, in particular having an elongated rod-shaped body,
with a distal and a proximal end, whereby an application aid is
provided on the proximal end, whereby the application aid comprises
at least on its outer surface, in particular, optionally, on the
inner surface, at least in part, at least one additive selected
from metals, metal-containing compounds, and organometallic
compounds for affecting the polymerisation, in particular for
accelerating the polymerisation and/or for improving the chemical
resistance of the polymerised dental material. It is particularly
preferred in this context that a radical polymerisation is being
affected and/or accelerated. According to the invention, the
polymerisation of dental adhesives, such as self-etching adhesives,
in particular of dental monomers with at least one acid group,
preferably of dental adhesives with a pH value below pH=7,
preferably with a pH of 6 to 1, preferably of 5 to 1, is being
accelerated. The monomers for radical polymerisation having an acid
group in the molecule, also called acid component, comprise
polymerisable monomers with at least one, preferably multiple,
ethylene groups and at least one carboxylic acid, carboxylic acid
anhydride, phosphoric acid and/or sulfonic acid group, as disclosed
in more detail below.
[0008] Preferably, the adhesion of dental materials is improved
and/or the chemical compatibility with further dental materials is
improved. Preferably, the applicator can comprise a mixture of the
additives specified above. Advantageously, the applicator comprises
1 to 10 different additives, mixtures of said additives, activators
and/or excipients, in particular 1, 2, 3, 4, 5, 6, 7, 8, 9 or
10.
[0009] An improvement of the adhesion values has been demonstrated
for a particularly preferred micro-applicator that was provided
with platinum, preferably powdered platinum. To produce the
applicator, a commercial applicator was treated with an aqueous
nano-platinum suspension and dried. With regard to the applicator
thus treated, a beneficial effect in the course of a pretreatment
of the tooth surface in combination with Heraeus iBOND.RTM. Self
Etch was demonstrated. Compared to the reference experiments with
iBOND.RTM. Self Etch using a commercial applicator (treated without
platinum), statistically significantly higher results for the shear
bond strength when bonded to enamel were obtained when a
platinum-treated applicator was used. The shear bond strength
results on enamel were increased by 10 to 20% with said
applicators. Accordingly, the total adhesion thus attained was
improved to reach a thus far unattainable range.
[0010] It is particularly preferred that the applicator or the
application aid is at least in part impregnated with
nano-particulate platinum, in particular on its outer surface
and/or on at least one inner surface. Also preferably, the
nano-particulate platinum has a particle size of less than or equal
to 10 nm, in particular the nano-particulate platinum is platinum
sponge. Particularly preferred particle sizes of the platinum
comprise particles of less than or equal to 50 nm, less than or
equal to 10 nm, 7 nm, approx. 5 nm with +/-2 nm. A platinum sponge
is particularly preferred. Preferably, the purity of the platinum
is more than or equal to 90% by weight of a platinum content, in
particular more than or equal to 95% by weight, 98% by weight, 99%
by weight, 99.5% by weight, further preferably more than or equal
to 99.7% by weight, 99.8% by weight, 99.9% by weight.
[0011] According to a preferred alternative, applicators comprising
at least one further additive in addition to a first additive, in
particular an activator, are provided. In this context, a
combination of platinum and a salt of a sulfinic acid, in
particular an alkaline salt of toluenesulfinic acid, is a preferred
combination of additives on the applicators. Using this
combination, it is feasible to have the application of compounds
that cannot be stored or are not compatible with a dental
composition still take place in a one-step application.
[0012] Accordingly, applicators were impregnated with platinum. The
resulting dried applicators were used to apply iBOND.RTM. Self Etch
to teeth, in particular into the cavity of said teeth, particularly
preferably in the context of a caries treatment. Samples of
iBOND.RTM., which were applied with untreated applicators, served
as reference. The shear bond strength on enamel was improved by
10-20% with the applicators comprising platinum as compared to the
values obtained with applicators with no additives. The applicators
according to the invention allow the adhesion of the dental
materials to be improved further using an application that is
unchanged for the user.
[0013] The beneficial effect of the additive on the improvement of
the shear bond strength is concentration-dependent, which is not
uncommon for catalyst systems. Since iBOND.RTM. Self Etch as such
predominantly causes cohesive fractures in the hard substance of
the tooth in shear bond strength tests on dentine with commercial
applicators, it was not feasible to demonstrate further improvement
of the adhesion by the additive-provided applicators using this
method. The control values for iBOND.RTM. Self Etch on dentine are
already at the upper limit of the range, in which the shear bond
strength is a suitable test method.
[0014] According to a preferred embodiment of the invention, at
least one additive has a particle size of less than or equal to 100
nm, in particular more than or equal to 1 nm. Alternatively or in
addition, at least one additive is present in nano-particulate
form, in particular having a particle size of less than or equal to
500 nm to more than or equal to 1 nm, preferably less than or equal
to 250 to 5 nm, particularly preferably less than or equal to 100
to 5 nm. Advantageously, the at least one additive comprises at
least one nano-particulate metal and/or at least one
metal-containing compound, preferably one additive comprises an
alkaline component, whereby the particle size thereof preferably is
less than or equal to 100 nm, such as from 100 to 1 nm.
[0015] According to an embodiment, a micro-applicator can comprise
a body having a distal and a proximal end, whereby an application
aid is provided on the proximal end and, preferably, a hand grip
element or a hand grip end is provided on the distal end.
[0016] A preferred applicator preferably consists of a polymer, in
particular of an inert polymer, which preferably is inert with
respect to dental materials, such as self-etching adhesives, in
particular the body of the applicator consists of said polymers.
Preferred polymers comprise thermoplastic polymers, in particular
comprising PE, PP, HDPE, LDPE, porous expanded polypropylene (PEPP)
and/or expanded polypropylene (EPP). The applicator preferably is
made of a flexible and, preferably, inert material, which, more
preferably, can be wetted well with dental materials.
[0017] Accordingly, it is preferred for the applicator to comprise,
on the proximal end of the body, an application aid that is at
least selected from a) filament, brush, sponge, flakes, comb, ball,
paintbrush, spatula, mixing pad, textile material and/or porous
means, in particular the additives can be present incorporated or
embedded in the porous means to be released upon contact with a
dental polymerisable composition. Advantageous applicators are made
of a thermoplastic polymer and/or a polymer that is chemically
resistant to solvents. Preferred application aids comprise a
multitude of filaments. It can be preferred that the applicator
comprises a rod-shaped and solid material body; in particular the
body of the applicator comprises no inner hollow space. Also
preferably, the body is at least partially cylindrical and of solid
material and/or conical and of solid material. According to the
invention, the applicator is a micro-applicator having a body with
a distal and a proximal end, whereby an application aid is provided
on the proximal end and, preferably, a hand grip element or a hand
grip end is provided on the distal end and the body of the
applicator is rod-shaped and of solid material.
[0018] According to a particularly preferred embodiment, the
application aid of the applicator is provided with at least one
catalytically active metal or at least one catalytically active
organometallic compound. Preferably, the metals are selected from
the metals of the platinum group. Particularly preferably, the at
least one catalytically active metal or the at least one
catalytically active organometallic compound is selected from iron,
cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium,
platinum, silver, copper, tin, and zinc, and the organometallic
compound is selected from complexes of the metals specified
above.
[0019] Moreover, according to the invention, the applicators can
comprise at least one additive or a mixture of said additives
selected from at least one metal-containing compound selected from
alkaline salts, alkaline earth salts; such as inorganic salts,
alkali metal hydroxides, alkaline earth metal hydroxides, organic
alkaline salts, organic alkaline earth salts; basic metal oxides,
base-forming agents, such as aluminium oxide, zinc oxide, copper
oxides, etc.; and metal-containing buffers. Further examples
comprise Ca(OH).sub.2, Nano-HAP, NaOH. The alkaline additives
enable an increase of the pH value, advantageously the pH value can
be increased by more than or equal to 0.2, 0.5 or 1.0, whereby
neutralisation upon the use with acidic dental materials is
particularly preferred.
[0020] The compounds stated below and applied to applicators are
considered to be an excipient: Carboxylic acids, salt of a
carboxylic acid, fruit acid, buffer and/or base. Said compounds can
have a stabilising effect on the suspension for production of the
applicators and can be impregnated onto the applicators. Introduced
by means of the applicator, they can act as a buffer in a
self-etching dental material.
[0021] The object of the invention also includes applicators having
at least one additive or a mixture of said additives comprising
bases, base-releasing compounds selected from metals,
metal-containing compounds, and organometallic compounds comprising
alkali hydroxide, alkaline earth hydroxide, neutral bases, anionic
bases, cationic bases, metal oxide, base-forming agents, such as
CaO, sodium hydrogencarbonate, aluminium hydroxide, or with at
least one further additive comprising organic bases and/or
ammonia.
[0022] The buffers can be selected, inter alia, from acetic
acid-acetate buffer (pH 3.7 to 5.7), phosphate buffer (pH 5.4 to
8.0), ammonia buffer (pH 8.2 to 10.2), citric acid buffer or
citrate buffer, TRIS: Tris(hydroxymethyl)-aminomethane (pH 7.2 to
9.0), HEPES: 4-(2-hydroxyethyl)-1-piperazinethanesulfonic acid (pH
6.8 to 8.2), HEPPS: 4-(2-Hydroxyethyl)-piperazine-1-propanesulfonic
acid (pH 7.3 to 8.7), MES: 2-(N-morpholino)ethanesulfonic acid (pH
5.2 to 6.7), barbital-acetate buffer according to Michaelis (pH 2.6
to 9.2) or a lactic acid buffer system.
[0023] A compound serving as activator or as further additive that
can be applied to the applicator can comprise the following
compounds or mixtures: aromatic organic acid and/or a salt thereof,
such as, for example, an organic sulfinic acid and/or a salt
thereof or barbituric acid and/or a derivative thereof. The organic
sulfinic acid or a salt thereof is sulfinic acid or a common alkali
metal salt, alkaline earth metal salt, amine salt or ammonium salt
of sulfinic acid. A lithium, sodium, potassium salt or the like can
be selected as alkali metal salts. Magnesium, calcium, strontium or
a barium salt or the like can be selected as alkaline earth metal
salt. A conceivable amine salt is a primary amine salt such as, for
example, methylamine, ethylamine, propylamine, butylamine, aniline,
toluidine, phenylene diamine or xylylene diamine; a secondary amine
salt such as, for example, dimethylamine, diethylamine,
dipropylamine, dibutylamine, piperidine, N-methylaniline,
N-ethylaniline, diphenylamine or N-methyltoluidine; or a tertiary
amine such as, for example, trimethylamine, triethylamine,
pyridine, N,N-dimethylaniline, N,N-di(hydroxyethyl)aniline,
N,N-diethylamine, N,N-dimethyltoluidine, N,N-diethyltoluidine or
N,N-(hydroxyethyl)toluidine. Typical ammonium salts comprise an
ammonium, tetramethylammonium, tetraethylammonium,
tetrapropylammonium salt or trimethylbenzylammonium salt.
[0024] Preferred examples of an organic sulfinic acid include
alkanesulfinic acids such as, for example, ethanesulfinic acid,
propanesulfinic acid, hexanesulfinic acid, octanesulfinic acid,
decanesulfinic acid, and dodecanesulfinic acid; alicyclic sulfinic
acids such as, for example, cyclohexanesulfinic acid.
[0025] The activator can be selected from the following aromatic
organic acids and/or a salt, in the kit selected from an aromatic
organic acid and/or a salt thereof such as, for example, an organic
sulfinic acid and/or a salt thereof or barbituric acid and/or a
derivative thereof. Conceivable salts of sulfinic acid include the
above-mentioned alkaline or alkaline earth salts, amine as well as
ammonium salts.
[0026] Advantageous sulfinic acids comprise, as organic sulfinic
acid, an alkanesulfinic acid such as, for example, ethanesulfinic
acid, propanesulfinic acid, hexanesulfinic acid, octanesulfinic
acid, decanesulfinic acid, and dodecanesulfinic acid; alicyclic
sulfinic acids such as, for example, cyclohexanesulfinic acid and
cyclooctanesulfinic acid; as well as aromatic sulfinic acids such
as, for example, benzenesulfinic acid, o-toluenesulfinic acid,
p-toluenesulfinic acid, ethylbenzenesulfinic acid,
decylbenzenesulfinic acid, dodecylbenzenesulfinic acid,
chlorobenzenesulfinic acid, and naphthalinesulfinic acid.
[0027] Preferred examples of the organic sulfinates comprise
lithiumbenzenesulfinate, sodiumbenzenesulfinate,
potassiumbenzenesulfinate, magnesiumbenzenesulfinate,
calciumbenzenesulfinate, strontiumbenzenesulfinate,
bariumbenzenesulfinate, butylaminebenzenesulfinate,
anilinebenzenesulfinate, toluidinebenzenesulfinate,
phenylendiaminebenzenesulfinate, diethylaminebenzenesulfinate,
diphenylaminebenzenesulfinate, triethylaminebenzenesulfinate,
ammoniumbenzenesulfinate, tetramethylammoniumbenzenesulfinate, and
trimethylbenzylammoniumbenzenesulfinate. Moreover, also conceivable
are lithium-o-toluenesulfinate, sodium-o-toluenesulfinate,
potassium-o-toluenesulfinate, calcium-o-toluenesulfinate,
cyclohexylamine-o-toluenesulfinate, aniline-o-toluenesulfinate,
ammonium-o-toluenesulfinate, tetraethylammonium-o-toluenesulfinate,
lithium-p-toluenesulfinate, sodium-p-toluenesulfinate,
potassium-p-toluenesulfinate, p-toluenesulfinic acid,
barium-p-toluenesulfinate, ethylamine-p-toluenesulfinate,
toluidine-p-toluenesulfinate, N-methylaniline-p-toluol-sulfinate,
pyridine-p-toluenesulfinate, ammonium-p-toluenesulfinate,
tetramethylammonium-p-toluenesulfinate,
sodium-naphthalinesulfinate, strontium-naphthalinesulfinate,
triethylamine-naphthalinesulfinate,
N-methyltoluidine-naphthalinesulfinate,
ammonium-naphthalinesulfinate,
trimethylbenzyl-ammonium-naphthalinesulfinate and the like for use
as organic sulfinate. Sodium-toluenesulfinate is particularly
preferred.
[0028] Likewise, the at least one activator can be selected from a
barbituric acid derivative. The activator in the kit can be
selected from a barbituric acid derivative. The barbituric acid
derivatives are advantageously selected from
1,3,5-trimethylbarbituric acid, 1,3,5-triethylbarbituric acid,
1,3-dimethyl-5-ethylbarbituric acid, 1,5-dimethylbarbituric acid,
1-methyl-5-ethylbarbituric acid, 1-methyl-5-propylbarbituric acid,
5-ethylbarbituric acid, 5-propylbarbituric acid, 5-butylbarbituric
acid, 5-methyl-1-butylbarbituric acid, 1-benzyl-5-phenylbarbituric
acid, 1-cyclohexyl-5-ethylbarbituric acid or an alkali metal salt
thereof. Preferred concentrations of the barbituric acid derivative
range from 0.1-10% by weight based on the total composition of the
dental adhesive.
[0029] The above-mentioned activators, such as aromatic organic
acids or barbituric acid derivatives, are preferably dissolved
alone under neutral or alkaline conditions. The impregnation of the
applicator can take place by means of dipping, spraying as well as
any other method common to a person skilled in the art. Spraying a
tacky powder is feasible just as well. Depending on the planned
application, the at least one additive can be applied together with
further excipients that affect the time of release of the at least
one additive. This can be a delaying or an accelerating, for
example by adding disintegration agents.
[0030] Further additives, which are also suitable and can be
provided on the activator additionally or alternatively, comprise
an excipient, activator and/or at least one further additive,
whereby the excipients comprise carboxylic acid, salt of a
carboxylic acid, fruit acid, buffer, hygroscopic compounds, in
particular hygroscopic salts, such as (CaCl.sub.2), and/or the at
least one additional further additive is selected from bases and
bases-releasing compounds.
[0031] Depending on the stability of the additives, the applicators
are packaged individually or together in airtight and/or
light-protected manner. Preferably, the applicators are packaged in
a blister, etc., that protects from light and/or is airtight.
[0032] Another object of the invention is a method for producing a
dental micro-applicator, as well as an applicator obtainable
according to said method, in particular an applicator as described
above, in which
(i) a dental micro-applicator having a body with a distal and a
proximal end with an application aid on the proximal end (ii) the
application aid is contacted to with at least one additive selected
from metals, metal-containing compounds, and organometallic
compounds for affecting the adhesion of dental materials.
[0033] Advantageously, the at least one additive is provided in
(ii) a suspension, dispersion, paste, solution, spray drying or the
at least one additive is provided in the form of a powder.
[0034] Moreover, it is preferred to contact the application aid
with a nano-particulate additive in step (ii). It is preferred in
this context for the additive, in particular the metallic additive,
particularly preferably platinum, to preferably be present having a
particle size of less than or equal to 500 nm to more than or equal
to 1 nm, preferably less than or equal to 250 to 5 nm, particularly
preferably less than or equal to 100 to 5 nm or of 50 to 2 nm.
Advantageously, at least one nano-particulate metal and/or at least
one nano-particulate metal-containing compound is being provided.
Preferably, an alkaline component, in particular one having a
particle size of less than or equal to 100 nm, can be used. As
mentioned above, the at least one additive for contacting
preferably has a particle size of less than or equal to 100 nm and
is present, in particular, in a suspension. Alternatively, the
additives can be used in the method in the form of a solution, such
as aqueous solution, or a mixture of solvent/water. Particularly
preferably, the nano-particulate metal is used in a suspension in
(ii) in the method.
[0035] According to a particularly preferred variant of the method,
the metal is used in a suspension at a content, based on the total
composition of the suspension, of 1.0 to 1.010.sup.-8% by weight,
in particular of 1.010.sup.-1 to 1.010.sup.-8% by weight,
preferably of 1.010.sup.-3 to 1.010.sup.-5 by weight, particularly
preferably of 1.010.sup.-3 to 2.510.sup.-4% by weight, according to
the invention 1.010.sup.-3 to 2.210.sup.-3% by weight.
[0036] According to the invention, in the method for producing the
applicator, it is preferred to contact an applicator with the (ii)
application aid with at least one additive comprising at least one
metal-containing compound that is selected from alkaline salts,
alkaline earth salts, inorganic salts of alkali metals, inorganic
salts of alkaline earth metals; in particular, alkali metal
hydroxides, alkaline earth metal hydroxides; organic alkaline
salts, organic alkaline earth salts, basic metal oxides,
base-forming agents, and metal-containing buffers.
[0037] It is preferable to dry the impregnated applicators.
[0038] An other object of the invention is a kit comprising an a)
applicator as described above or obtainable by a method according
to the invention, and b) a dental adhesive, in particular a
polymerisable dental adhesive. The kit preferably comprises a) an
applicator comprising at least one additive selected from metals,
metal-containing compounds, and organometallic compounds for
affecting the adhesion of dental materials, in particular at least
platinum, in particular platinum sponge. Preferably, the applicator
in the kit comprises further additives such as an activator such as
a sulfinic acid or a salt of a sulfinic acid and/or a base.
Additives according to the invention are preferably self-etching
dental adhesives.
[0039] Preferably, the dental adhesive comprises at least A) one
radically polymerisable monomer having an acid group in the
molecule, B1) optionally, a photo-sensitiser and/or, optionally,
B2) a peroxide, C) a water-miscible solvent such as alcohol,
ketone, ester, ketal, isopropylidene glycerol, ethanol, preferably
acetone; and D) water.
[0040] Moreover, the kit can comprise E) at least one radically
polymerisable monomer without an acid group, which preferably is
not or poorly soluble in water (less than 2 g/100 ml H.sub.2O).
[0041] The monomers for radical polymerisation having an acid group
in the molecule according to A), also called acid component,
comprise polymerisable monomers with at least one, preferably
multiple, ethylene groups and at least one carboxylic acid,
carboxylic acid anhydride, phosphoric acid group and/or sulfonic
acid group.
[0042] Mono-functional polymerisable monomers with a carboxylic
acid group or a carboxylic acid anhydride group in the molecule can
be selected from mono-carboxylic acids, di-carboxylic acids,
tri-carboxylic acids, tetra-carboxylic acids, poly-carboxylic
acids, and anhydrides thereof. Preferred compounds can be
carboxylic acids and/or anhydrides such as maleic acid,
p-vinylbenzoic acid, 11-(meth)acryloyloxy-1,1-undecandicarboxylic
acid (MAC-10), 1,4-di(meth)acryloyloxyethylpyromellithic acid,
6-(meth)acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid,
4-(meth)acryloyloxymethyltrimellithic acid and anhydrides thereof,
4-(meth)acryloyloxyethyltri mellithic acid and anhydride thereof,
4-(meth)acryloyloxybutyltrimellithic acid and anhydride thereof,
4-[2-hydroxy-3-(meth)acryloyloxy]butyltrimellithic acid and
anhydride thereof,
2,3-bis(3,4-dicarboxybenzoyloxy)propyl(meth)acrylate, 2-, 3-, or
4-(meth)acryloyloxybenzoic acid, N-O-di(meth)acryloyloxytyrosine,
O-(meth)acryloyloxytyrosine, N-(meth)acryloyloxytyrosine,
N-(meth)acryloyloxyphenylalanine, N-(meth)acryloyl-p-amine-benzoic
acid, N-(meth)acryloyl-O-aminebenzoic acid, adduct of
glycidyl(meth)acrylate and N-phenylglycine or N-tolylglycine,
4-[(2-hydroxy-3-(meth)acryloyloxypropyl) amino] phthalic acid, 3-
or
4-[N-methyl-N-(2-hydroxy-3-(meth)acryloyloxypropyl)amino]phthalic
acid, (meth)acryloylaminosalicylic acid and
(meth)acryloyloxysalicylic acid.
11-(Meth)acryloyloxy-1,1-undecanedicarboxylic acid (MAC-10) and
4-methacryloyloxyethyltrimellithic acid (4-MET) or the anhydride
thereof (4-META) are preferred. Poly-functional polymerisable
monomers with at least two carboxyl groups in the molecule that can
be used as component (A) can comprise di-carboxylic acids,
tri-carboxylic acids, tetra-carboxylic acids and derivatives
thereof such as, for example, an addition product of
2-hydroxyethyl-(meth)acrylate and pyromellithic acid dianhydride
(PMDM), an addition reaction product of 2 mol
hydroxyethyl-(meth)acrylate and 1 mol maleic acid anhydride or
3,3',4,4'-benzophenonetetracarboxylic acid dianhydride (BTDA) or
3,3',4,4'-biphenyltetracarboxylic acid dianhydride, and
2-(3,4-dicarboxybenzoyloxy)1,3-di(meth)acryloyloxypropane.
[0043] Polymerisable monomers having at least one phosphoric acid
group in the molecule comprise, for example,
2-(meth)acryloyloxyethyl acid phosphate, 2- and
3-(meth)acryloyloxypropyl acid phosphate, 4-(meth)acryloyloxybutyl
acid phosphate, 6-(meth)-acryloyloxyhexyl acid phosphate,
8-(meth)acryloyloxyoctyl acid phosphate, 10-(meth)-acryloyloxydecyl
acid phosphate, 12-(meth)acryloyloxydodecyl acid phosphate,
bis({2-(meth)-acryloyloxyethyl} acid phosphate, bis {2 or
3-(meth)acryloyloxypropyl}-acid phosphate,
2-(meth)acryloyloxyethylphenyl acid phosphate,
2-(meth)acryloyloxyethyl-p-methoxyphenyl-acid phosphate and the
like. The phosphoric acid in these compounds can be replaced by a
thiophosphoric acid group.
[0044] Among the monomers specified above, the following are
preferred: 2-(meth)acryloyloxyethyl-phenyl acid phosphate and
10-(meth)acryloyloxydecyl acid phosphate. The monomers having a
phosphoric acid group can be used individually or in
combination.
[0045] Polymerisable monomers having a sulfonic acid group in the
molecule can comprise 2-sulfoethyl(meth)acrylate, 2- or 1-sulfo-1-
or -2-propyl(meth)acrylate, 1- or 3-sulfo-2-butyl-(meth)acrylate,
3-bromo-2-sulfo-2-propyl(meth)acrylate,
3-methoxy-1-sulfo-2-propyl(meth)-acrylate,
1,1-dimethyl-2-sulfoethyl(meth)acrylamide, and
2-methyl-2-(meth)acrylamidpropanesulfonic acid, whereby
2-methyl-2-(meth)acrylamidpropanesulfonic acid is preferred.
[0046] The polymerisable monomer A) can comprise an acid group that
is present as a salt such as, for example, as monovalent or
polyvalent metal salt or ammonium salt. However, it is preferred in
this context that the monomer A) acts as an acid when it is used in
conjunction with another acidic compound and is contacted to the
other acidic compound. The preceding components A) can be used
individually or in combination with each other.
[0047] Preferred components B1) and/or B2) optionally comprise a
photo-sensitiser as B1) and/or optionally comprise a peroxide as
B2).
[0048] Preferred components B1) comprise an alpha-ketocarbonyl
compound or an acylphospine oxide compound. Actually preferred are
alpha-diketone, alpha-ketoaldehyde, alpha-ketocarboxylic acid,
alpha-ketocarboxylate. Actually preferred are alpha-diketones, such
as, for example, diacetyl, 2,3-pentadione, 2,3-hexadione, benzyl,
4,4'-dimethoxybenzyl, 4,4'-diethoxybenzyl, 4,4'-oxybenzyl,
4,4'-dichlorobenzyl, 4-nitrobenzyl, alpha-naphthyl, camphor
quinone, camphor quinone sulfonic acid, camphor quinone carboxylic
acid, and 1,2-cyclohexanedione; alpha-ketoaldehydes, such as, for
example, methylglyoxal and phenylglyoxal; and others, such as, for
example, pyruvic acid, benzoylformic acid, phenylpyruvic acid,
methylpyruvate, ethylbenzoylformate, methylphenylpyruvate, and
butylphenylpyruviate. Alpha-diketones are particularly preferred
due to their stability, as are diacetyl, benzyl, and camphor
quinone.
[0049] Moreover, component B1) comprises benzoyldimethoxyphosphine
oxid, benzoylethoxyphenylphosphine oxide,
2-methylbenzoyldiphenylphosphine oxide,
2,4,6-trimethyl-benzoyldiphenylphosphine oxide and the derivatives
thereof. All photo-active compounds can be used individually or as
a mixture.
[0050] Compounds such as diacetyldiperoxide, dipropylperoxide,
dibutylperoxide, dicaprylperoxide, dilaurylperoxide,
benzoylperoxide (BPO), p,p'-dichlorobenzoylperoxide,
dimethoxybenzoylperoxide, p,p'-dimethylbenzoylperoxide, and
p,p'-dinitrodibenzoylperoxide; and inorganic peroxides, such as,
for example, ammonium persulfate, potassium persulfate, potassium
chlorate, potassium bromate, and potassium perphosphate can be used
as peroxide B2). BPO is preferred.
[0051] Alcohol, ketone, ester, ketal, isopropylidene glycerol, such
as ethanol, but preferably acetone, can be used as component C), a
water-miscible solvent.
[0052] Component C) according to the invention is a water-soluble
organic solvent. It serves for homogeneous dissolution or
dispersion of any of the above-mentioned components, whereby the
solvent is to be inert to the components and, advantageously, is
volatile. Higher alcohols can be used as well, such as, for
example, ethylene glycol, propylene glycol, and glycerol.
[0053] Component E) preferably comprises at least one monomer for
radical polymerisation devoid of an acid group, which, in
particular, is not or poorly soluble in water. Preferred monomers
for radical polymerisation devoid of an acid group that are
different from component A) comprise aromatic vinyl compounds, such
as, for example, styrene and divinylbenzende, vinylester such as
for example vinylacetate; aliphatic esters of (meth)acrylic acid,
such as, for example, methyl(meth)acrylate, ethyl(meth)acrylate,
propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate,
hexyl(meth)acrylate, neopentylglycoldi(meth)acrylate, and
trimethylolpropane-tri(meth)acrylate; aromatic esters such as, for
example, phenyl(meth)acrylate; aromatic (meth)acrylates such as,
for example, 2-hydroxy-3-phenoxypropyl(meth)acrylate, an adduct of
1 mol bisphenol A and 2 mol glycidyl(meth)acrylate (Bis-GMA), a
condensate of 1 mol of an addition polymer made of bisphenol A with
glycidylether and 2 mol (meth)acrylic acid, and a condensate of 1
mol of an adduct of bisphenol A with ethylene oxide and 2 mol
(meth)acrylic acid (number of addition chains of ethylene oxide
m+n=2.6); urethane-bond-containing methacrylates such as, for
example, 2-(meth)acryloyloxy-ethylisocyanate and an adduct (UDMA)
made of 2 mol hydroxy-ethyl(meth)acrylate with 1 mol 2,2,4-(or
2,4,4-) trimethyl-1,6-hexamethylene-diisocyanate; aliphatic
(meth)acrylic acid esters such as, for example,
1,6-hexamethylene-dimethacrylate (1,6-HX),
neopentylglycoldi(meth)acrylate, and
trimethylolpropane-tri(meth)acrylate; polyethylene
glycol-di(meth)acrylates (chain length n=less than 6) such as, for
example, ethylene glycol-di(meth)acrylate, diethylene
glycol-di(meth)acrylate, and triethylene glycoldi(meth)acrylate;
and polypropylene glycoldi(meth)acrylates (chain number n=12 or
less) such as, for example, propylene glycol-di(meth)acrylate,
dipropylene glycoldi-(meth)acrylate, tripropylene
glycoldi(meth)acrylate, and nanopropylene glycol-di(meth)acrylate.
Components E) according to the invention comprise monomers that
comprise at least one (meth-)acrylate group selected from
methylmethacrylate, ethyl-methacrylate, propylmethacrylate,
butylmethacrylate, n-hexylmethacrylate,
2-phenoxy-ethylmethacrylate, isobornylmethacrylate,
isodecylmethacrylate, polypropylene glycol-mono-methacrylate,
tetrahydrofuryl-methacrylate, polypropylen
glycol-mono-methacrylate, methylacrylate, ethylene acrylate,
propylacrylate, butylacrylate, n-hexylacrylate,
2-phenoxyethylacrylate, isobornylacrylate, isodecylacrylate,
polypropylene glycol-mono-acrylate, tetrahydrofuryl-acrylate,
hydroxyethylacrylate, hydroxy-propylacrylate,
hydroxyethyl-methacrylate, hydroxypropylmethacrylate or mixtures
thereof or at least one cross-linker. Typical cross-linkers are
BDMA, 1,4-butanediol-dimethacrylate (1,4-BDMA) or
pentaerythritol-tetraacrylate, urethanedimethacrylate (UDMA),
bis-GMA monomer (bisphenyl-A-glycidyl-methacrylat). The use of
diluents (low viscosity acrylates such as triethylene
glycoldimethacrylate (TEGDMA) and diethylene glycoldimethacrylate
(DEGMA), etc.
[0054] Preferred (meth-)acrylates having at least two
(meth-)acrylate groups are selected from ethanedioldimethacrylate,
tetraethylene glycoldimethacrylate, diethylene glycol
dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol
dimethacrylate (400) or (600), butanedioldimethacrylate,
hexanedioldimethacrylate, decanedioldimethacrylate,
dodecanedioldimethacrylate, 1,3-butylene glycol dimethacrylate,
dipropylglycolmethacrylate, bisphenol-A-dimethacrylate,
bisphenol-A-dimethacrylate derivative such as ethoxylated
2-bisphenol-A-dimethacrylate, trimethylolpropane trimethacrylate,
triethylene glycol dimethacrylate,
2,2-bis-4-(3-methacryloxy-2-hydroxy-propoxy)-phenyl propane
(Bis-GMA), tricyclodecane dimethanoldimethacrylate, a
urethanemethacrylate with at least two methacrylate groups or a
mixture containing at least one of said (meth-)acrylates.
[0055] Preferred (meth-)acrylates with three to six (meth-)acrylate
groups are selected from (i) with three (meth-)acrylate groups from
ethoxylated (15)-trimethylolpropane-triacrylate, ethoxylated
5-pentaerythritoltriacrylate, propoxylated
(5.5)-glyceryltriacrylate, trimethylol-propanetrimethacrylate,
tris(2-hydroxyethyl)-isocyanurate-triacrylate, and/or (ii) with
four (meth-)acrylate groups from di-tri
methylolpropane-tetraacrylate, ethoxylated
(4)-pentaerythritol-tetraacrylate, pentaerythritol-tetraacrylate,
di-trimethylolpropane-tetramethacrylate, ethoxylated
(4)-pentaerythritol-tetramethacrylate,
pentaerythritol-tetramethacrylate and/or (iii) with five
(meth-)acrylate groups from di-pentaerythritol-pentaacrylate,
i-pentaerythritol-pentamethacrylate, dipentaerythritol
pentaacrylate, di(tetramethylolmethane)-pentamethacrylate, and/or
(iv) with six (meth-)acrylate groups a
dipentaerythrit-hexa(meth)acrylate. Also well-suited are oligomers
of (meth-)acrylates, in particular urethane-di-acrylate
oligomer.
[0056] Another object of the invention is a kit comprising an
applicator that comprises at least one further additive selected
from metals, metal-containing compounds and organometallic
compounds, in particular alkali hydroxide, alkaline earth
hydroxide, aluminium hydroxide, zinc oxide, alkaline salts or
alkaline earth salts of organic compounds.
[0057] Another object of the invention is the use of at least one
additive selected from metals, metal-containing compounds, and
organometallic compounds for affecting the adhesion of dental
materials, whereby the additive is provided at or on an application
aid by contacting the at least one additive to a polymerisable
dental adhesive. Preferably, the polymerisable dental adhesive can
be applied to a dental surface by means of the application aid.
[0058] Another subject matter of the invention is the use of at
least one adhesive selected from metals, metal-containing
compounds, and organometallic compounds for affecting the
polymerisation, in particular the polymerisation of dental
materials, such as dental adhesives, comprising at least one
polymerisable monomer having an acid group in the molecule,
preferably the radical polymerisation of dental materials, in
particular containing monomers with an acid group, whereby the
additive is provided at or on an application aid by contacting the
at least one additive to a polymerisable dental adhesive.
[0059] The monomers for radical polymerisation having an acid group
comprise (meth)acrylate(s) and/or olefinic urethane-based dental
monomers.
[0060] The invention is illustrated in more detail in the following
based on examples, without limiting it to said examples:
Example 1
Nano-Platinum Micro-Applicator (Presently: Microbrushes.RTM.)
Impregnation of the Microbrush:
[0061] The micro-applicators (Microbrush; commercial, untreated)
were suspended by their flocked side in the impregnation solution
(nano-platinum suspension with a platinum content of 0.002%) for 24
h. The suspension was stirred during the impregnation to effect
homogeneous distribution of the Pt particles.
[0062] Subsequently, the impregnated micro-applicators were dried
in a heating cabinet at 37.degree. C. for 24 h. The impregnation
cannot be quantified by weighing with an analytical balance.
However, the impregnation of the micro-applicators is evident by
the clear grey colouration.
Test of the Efficacy of the Impregnated Micro-Applicators:
[0063] Test A) Tests of Adhesion Between Enamel and Composite
(Shear Bond Strength, SBS)
[0064] Tooth substrate: Enamel; human tooth
[0065] Adhesive: Heraeus Kulzer GmbH iBOND.RTM. Self Etch
[0066] Composite: Heraeus Dental Venus.RTM. Diamond A2
Microbrush for application of the adhesive:
[0067] 1. Untreated as a reference
[0068] 2. Impregnated with nano-platinum solution
[0069] Measuring procedure--SBS test on enamel: The adhesive was
processed on polished enamel in accordance with the instructions
for use. Subsequently, the composite was applied appropriately with
a receiving device (Ultradent device, cf. EN ISO 29022) and
polymerised such that a composite cylinder with a diameter of 2.38
mm was produced.
[0070] After storage for 24 h at 37.degree. C. in water, the test
bodies were affixed in the Zwick Z010 universal testing machine
using a test clamping device (cf. EN ISO 29022). The testing
machine was controlled by a PC using the Zwick testXpert software.
The test was done at an advancing rate of 1.0 mm+/-0.1 until the
bond between tooth and composite cylinder fractured.
[0071] The force transferred to the measuring can during the test
procedure was measured by the PC and registered as shear bond
strength in MPa by the software.
[0072] Overview of the analysis of the data and results of the
adhesion tests: A total of 2 series of measurements of iBOND.RTM.
Self Etch with the nano-platinum microbrush and were compared to
the reference iBOND.RTM. Self Etch with untreated micro-applicator.
The adhesion tests yielded means of 29.3 MPa for the reference and
35.9 MPa and 36.0 MPa for the nano-platinum micro-applicator
(Microbrush) tests.
SBS [MPa] iBOND.RTM. Self Etch on Enamel
TABLE-US-00001 Series of measurements Reference with nano-platinum
untreated Micro-applicators Micro-applicators Test 1 Test 2 Mean
29.3 35.9 36.0 Standard deviation 1.8 7.6 1.8
[0073] The use of the nano-platinum-impregnated microbrush
(micro-applicator) allows a significantly higher adhesion, mean of
up to 23%, on enamel to be attained.
[0074] Test B: Polymerisation Turnover and/or Double Bond Turnover
After Illumination
[0075] Adhesive: HeraeusDental iBOND.RTM. Self Etch
[0076] Composite: HeraeusDental Venus A2
[0077] Light unit: HeraeusTranslux Powerblue
Microbrush for application of the adhesive:
[0078] 1. Untreated as a reference
[0079] 2. Impregnated with nano-platinum solution
Measuring Procedure for the Double Bond Conversion Rate:
[0080] The conversion rate (percentage of converted double bonds)
was determined using an FTIR-ATR Diamond Spectrometer (Spectrum
One, Universal ATR Sample Accessory, Perkin Elmer).
[0081] The FTIR spectra were measured right away and 10 minutes
after polymerisation of the adhesive and filling of a virtual
cavity (filling covers the ATR crystal, h=1.6 mm) with the Venus
composite. The conversion rate was calculated from the ratio of the
absorption bands of the unpolymerised aliphatic carbon double bond
(wavelength=1638 cm.sup.-1) versus the polymerised carbon double
bond.
[0082] The spectra were analysed by a derivative manner using the
2nd derivative with smoothing of points over the entire height of
the aliphatic carbon double bond peak at 1638 cm.sup.-1. The
adhesive was applied to the ATR crystal with the untreated
microbrush as the reference and the nano-platinum microbrush as
follows: Two droplets of bonding were placed in a mixing bowl. The
adhesive was stirred with the microbrush for 10 seconds and then
applied in two aliquots to the ATR crystal. The solvent was
evaporated for 15-20 seconds and then exposed to an air blower (5
bar) for 20 seconds such that a rigid film was formed.
[0083] The non-polymerised adhesive film was covered with a black
hood for protection from light and the non-polymerised spectrum was
recorded. A template h=1.6 mm was placed; the adhesive film over
the ATR crystal was polymerised for 20 seconds. Then the Venus A2
composite was layered over the adhesive film, the composite was
covered with a film (permeable to the activated radiation) and
polymerisation took place for 20 seconds. A polymerised spectrum
was recorded right away <immediately after illumination> and
after 10 minutes.
[0084] Overview of the results of the determination of the adhesive
conversion rate: The series of measurements of iBOND.RTM. Self Etch
processed with the nano-platinum microbrush.RTM. was compared to
the reference iBOND.RTM. Self Etch with untreated microbrush.RTM..
The conversion rates were determined right after the polymerisation
and 10 minutes after the polymerisation as the mean of 5
measurements each.
Double Bond Conversion % of iBOND.RTM. Self Etch Right Right After
Illumination
TABLE-US-00002 Micro-applicator Micro-applicators Mean 58.5 69.0
Standard deviation 3.1 5.2
[0085] The use of the nano-platinum-impregnated micro-applicators
(Microbrush.RTM.) allows a clearly higher double bond conversion
rate to be attained right after illumination.
Double Bond Conversion % of iBOND.RTM. Self Etch Right 10 Minutes
After Illumination
TABLE-US-00003 Reference untreated Nano-platinum micro-applicators
micro-applicators Mean 63.8 74.9 Standard deviation 3.0 4.6
[0086] The use of the nano-platinum-impregnated micro-applicators
allows a significantly higher double bond conversion rate to be
attained.
Example 2
Basic Micro-Applicators (Microbrushes.RTM.)
[0087] The low pH value of all-in-one adhesives prevents the
bonding of self-curing materials partially or even completely. For
this reason, the adhesive should use alkaline-impregnated MBs to be
capable of conditioning enamel/dentine for a period of time in
order to be neutral and/or less acidic during the application time
of 20 seconds and enable the bonding of self-curing materials.
[0088] Micro-applicators (Microbrush) impregnated with Ca(OH).sub.2
solution were produced and used to apply the iBOND Self Etch
adhesive.
[0089] Production of impregnated micro-applicators (20 Microbrush):
A total of 50 ml 15% aqueous calcium hydroxide solution (calcium
hydroxide in water pa.=slightly saturated solution) was produced
and the flocked part of the micro-applicators (Microbrush.RTM.,
brush) was dipped in the solution for 1 h while stirring. Then
followed a drying process for 24 h in a heating cabinet at
37.degree. C., the parts were suspended for drying. The handles of
the micro-applicators were cleaned.
[0090] The efficacy was tested by measuring the pH value as a
function of the contact time with the adhesive. For this purpose,
the pH value of the adhesive was determined before contact with the
impregnated micro-applicators as well as after 1 second, 10 seconds
and 20 seconds. As a control, the pH value was determined after 10
and 20 seconds of contact time with untreated micro-applicators
(Microbrush.RTM.). According to the instructions for use, iBOND
Self Etch is to be massaged into the hard substance of the tooth
with a micro-applicator for 20 s such that these time windows are
representative of the actual application time.
[0091] Devices/materials: WTW Microprocessor pH ION Meter; Schott
Instruments Electrode blue Line 16 pH SN Al 15010019 (for small
volumes) Centrifuge vial 1.7 ml; Adhesive: iBOND Self Etch;
Microbrush.RTM. with Ca(OH).sub.2; Microbrush.RTM. untreated.
[0092] Measuring procedure: Placement of 40 droplets of adhesive.
Measurement of the pH value: Successively dip 10 MB
(micro-applicator; microbrush) for 1 second (keep MBs), measure pH
value for the contact time of 1 second The same MBs were then
dipped into the adhesive for another 9 s while stirring (keep MBs).
The pH value for the contact time of 10 s was measured. The same
MBs were then dipped into the adhesive for another 10 s while
stirring. The pH value for the contact time of 20 seconds was
measured.
TABLE-US-00004 Reference Ca(OH).sub.2-MB untreated MB Contact time
pH value pH value Without 1.55 1.55 1 second 1.64 -- 10 seconds
1.92 1.54 20 seconds 2.00 1.56
[0093] The use of the calcium hydroxide-impregnated
micro-applicators allows a delaying effect on the pH value to be
attained. The pH value can be increased significantly within the
time window of the application of adhesive.
* * * * *