United States Patent (19) 11) 4,192,795

Madhavan et al. 45) Mar. 11, 1980

54 BARUMALUMNUM SILICATE FILLER (56) References Cited
FOR U.V. CURABLE COMPOSITES U.S. PATENT DOCUMENTS
3,539,533 11/1970 Lee et al. . ..... 260/42.52
75 Inventors: Narayanan Madhavan, Dearborn 3,766,132
3,801,324
10/1973 Lee et al. .......................... 260/42.52
4/1974 Dietz ........................................ 32/15
Heights; Frank H. Freeman,
Farmington, both of Mich. 3,826,778 7/1974 Dietz ........................................ 32/15
3,911,581 10/1975 Dietz ................................. 260/42.52
3,973,972 8/1976 Muller ............................... 260/42.53
(73) Assignee: Sybron Corporation, Rochester, N.Y. 3,974, 104
3,975,203
8/1976 Foster et al. ......................... 252/478
8/1976 Dietz .................................... 106/299
21) Appl. No.: 837,787 Primary Examiner-Lewis T. Jacobs
Attorney, Agent, or Firm-Theodore B. Roessel; Owen
D. Marjama
22) Filed: Sep. 29, 1977
57 ABSTRACT
51 Int. Cl’................................................ C08K 3/40 A single paste photopolymerizable dental restoration
(52) U.S. C. .............................. 260/42.52; 260/42.15; composition which utilizes a barium-aluminum-silicate
260/998.11 glass filler material.
58 Field of Search ............. 260/42.15, 42.52, 998.11, 2 Claims, No Drawings
260/DIG. 36; 204/159.16
 4,192,795
1. 2
free radicals on exposure to actinic radiation, which
BARUMALUMNUM SILICATE FILLER FOR then react with the double bond of the monomer to
U.V. CURABLE COMPOSITES initiate polymerization. The resin used in the perpara
tion of this single paste may be derived from the reac
BACKGROUND OF THE INVENTION 5 tion of glycidyl ether of bisphenol A with methacrylic
Many dental restorative products are designed as two acid or acrylic acid:
H H CH3 H. H. CH3
HC-C-C-O C o-c-d-CH2 + 2CH2=C-COOH->
V / V /
O H CH3 H O
CH3 O H H
his
CH-c-3-o-c-ko-)--(y-o-c-
V H.
OH.
V
H. CH3 H. O.
-co-c-c=CH,
part systems, Specific quantities of the two parts, for
example, two pastes, are mixed together to initiate a This glycidyl methacrylate derivative of bisphenol-A is
chemical reaction which will result in the mixture solid known as bisphenol A-bis(3 methacrylato-2-hydroxy
ifying or setting to a hard rigid state, to cause the prod propyl)ether. The resin serves as a binder for the photo
uct to serve its intended purpose. The properties of the polymerizable dental composition, and is hereinafter
final product depend to a large extent upon how well referred to as Bis-GMA. Modification of this resin can
and how fast one performs the mixing. Failure to pro also be used or any other resin having polymerizable
duce a homogeneous mix may create irregularities ethylenic likages will work.
within the restoration. 25 The diluent monomer used may be selected from
The advent of low volatility, shelf stable, single paste alkyl methacrylates, alkylene dimethacrylates, trime
restorative products, which are activated by actinic thacrylates, alkyl acrylates, alkylene diacrylates, and
radiation permit the manufacture of a product which triacrylates. Some of the suitable monomers are repre
overcomes the above noted disadvantages associated sented by:
with two part systems. In the single paste photopolym 30 Triethyleneglycoldimethacrylate
erizable system, it is a continuing objective to match 1,6-hexanedioldiacrylate
materials which achieve a rapid cure rate which result 1,3-butylenedimethacrylate
in high strength restorations. One or more of these monomers can be used. The dilu
It is therefore an object of this invention to provide ent monomers copolymerize with Bis-GMA resin on
an improved dental process and product which exhibits 35 exposure to actinic radiation in the presence of a photo
advantages over the above noted two paste products. initiator and accelerator. The accelerator increases the
It is another object of the present invention to pro speed of the reaction.
vide a new composition and process for forming UV Another component present in the composite is a
initiated dental restorative materials which exhibit ac polymerization inhibitor which prevents the premature
celerated cure rates over conventional single paste ma polymerization of the Bis-GMA resin and diluent mon
terials. omer and is present only in small quantities. The suit
SUMMARY OF THE INVENTION able polymerization inhibitors are hydroquinons (HQ),
methyl ether of hydroquinone (MEHQ) and butylated
It has been discovered that the curing of photopolym hydroxytoluene (BHT).
erizable dental restoration composites are dramatically 45 The initiators used in this invention are alpha dike
affected by the composition of the filler material. The tones and their derivatives having the following general
use of barium-aluminum-silicate glass has shown a very formula:
unique and unexpected accelerating affect on the cure
rate of resin based cqmposites. In the U.V. spectrum R-CO-CO-R
range at about 3600 A, solid quartz is known to have 50
exceptional U.V. translucency, but particulate quartz Where R and R' can be same or different aliphatic or
does not induce the cure rates found with the particu aromatic groups and their derivatives. These photo
late barium-aluminum-silicate glass of the present inven initiators are slightly yellow in color. Since they are
tion. The unique application of the filler material of the present in small quantities, the final polymerized prod
present invention in U.V. initiated systems results in a 55 uct is almost colorless.
dental restoration composite which cures more rapidly Photo accelerators are chemical compounds which in
to a greater depth and which exhibits higher strengths the presence of initiators accelerates the photoreaction.
than conventional composites. The accelerators help polymerization penetrate a resto
DETALED DESCRIPTION OF THE ration placed into deep cavity preparation. The acceler
INVENTION ators are amines (primary, secondary and tertiary) and
diamines. Some examples are dimethylparatoluidines,
Photopolymerizable compounds suitable for use in N,N'-dimethylbenzylamine, N-methyldibutylamine,
the present invention comprise a monomer resin con triethylamine, trihexylamine, etc. Examples of diamine,
taining unsaturated sites which are capable of undergo N,N,N',N-tetra ethyl ethylenediamine and N,N,N',N'-
ing polymerization, a diluent monomer to control the 65 tetramethyl 1,6-hexanediamine.
viscosity of the resin, a filler or a combination of fillers, In the absence of the previously mentioned photo
an accelerator which increases the speed of photo reac initiators, these amines do not function to induce photo
tion of the composition, and an initiator which produces polymerization. Even though all amines in combination
 4,192,795
3 4.
with the previously mentioned photoinitiators acceler All these fillers are powdered until the particle size
ate to some extent, the tertiary amines (e.g., triethylam distribution of the fillers varies from about 5 to 40 mi
ine, trihexyl amine, etc.) are found to be the best for crons. These fillers are preferrably first silanated in
causing polymerization deep into the composite mass. order to increase the bonding between the inorganic
Amines with aromatic groups are not desirable as they filler and organic material. The bonding agent used is
impart a slight color on prolonged exposure to light. silane A-174 (y methacryloxy propyl trimethoxy
The photopolymerizable dental restorative product silane). The filler is treated with 50% of its weight of
may have from about 50 to 85% by weight refractory acetone, and 1% of A-174. The mixture is rolled in a
filler. According to the present invention, the filler ball mill for complete dispersion for an hour. The mix
comprises a barium-aluminum-silicate glass. A suitable 10 ture is poured in a try like vessel and allowed to settle
range of concentration comprises by weight 25-40% and the excess acetone decanted. The filler cake was
SiO2; 35-55% BaC); and 15-30% Al2O3. As will be dried in an oven at 280 F-300' F. for one hour at
more fully discussed later, the use of barium-aluminum temperature, ball milled one half hour, and sieved
silicate glass exhibits a unique and unexpected accelerat through a 160 mesh nitex cloth.
ing affect on the cure rate of the resin based composites. 15 When silanation is complete, a mono molecular coat
This results in a dental restoration composite which is ing of the bonding agent is formed on the filler surface.
easy and quick to cure and which exhibits higher The composites are made with 4.2 grams of BisCMA
strengths than conventional composites. resin

H. H.
g--o
OHH
fCH3 o----o-c-c=CH,
H OHH

The particle size distribution of the filler varies from

less than 5 to approximately 40 microns. The filler is
preferably silanated in order to increase the bonding
between the inorganic filler and the organic matrix 0.7 grams 1,6 hexane diacrylate
material. The silane bonding agents have a general for
mula RSiX3, R2Six2 and R3Six, where X may be halo 30
CH2=CH2COO(CH2)6OOCCH2=CH2
gen, alkoxy, or hydroxy group and R may be vinyl,
methacrylate, allyl, methallyl itaconate, maleate, acry 0.02 grams of benzil (C6H5CO CO C6H5)
late, itaconate, maleate acrylate aconitrate, fumarate, 0.05 grams of trihexylamine
alkyl, aryl, alkenyl crotonate, cinnamate and citracon
ate, sorbate or glycidyl groups. When silanation is com 35 The resin is mixed with the diluent monomer, photo
plete a mono molecular coating of the bonding agent is initiator and the accelerator. These are mixed well in a
present on the filler surface, which improves the adhe glass vessel by means of a Teflon (Reg. TM of duPont)
sion between the filler and the resin matrix. rod. When the mix is fairly uniform, 24 grams of bari
The following formulation was found to be satisfac um-aluminum-silicate filler is added and mixed well.
tory: Separate samples are also made using 16 grams of boro
barium-aluminum-silicate; 19.1 grams of lithium
aluminum-silicate; and 18.1 grams of fused quartz, re
Parts by Weight spectively. The variance in weight of the fillers allows
BisGMA (including MEHQ 200 ppm) 10-20 for their difference in density in order to insure that the
Diluent Monomer (including HQ 100 ppm) 2-5 volume of filler will be essentially the same in each
Benzil (purity 99.5%) 00-1 45 sample. The well mixed heavy paste is packed in a split
Trihexylamine .0-
Barium Aluminum Silicate Filler 70-85 cylindrical polytetrafluoroethylene mold, 12.5 mm high
by 6 mm diameter and open at both ends. The top and
The fillers examined during the development of the bottom Co)
were covered with Mylar (Reg. TM of duPont
strips and pressed to get a smooth surface. The
present invention comprise boro-barium-aluminum-sili Mylar covered ends were exposed for 15 seconds each
cate, lithium-aluminum-silicate, barium-aluminum-sili to the light emitted
cate, and fused quartz. The compositions of these fillers, sure mercury lamp atfrom Spectroline B-100 high pres
except for the fused quartz which is 100% SiO2, are of emission for this lamp is from of a distance 4 inches. The range
about 3000 to 4500 A.
shown in Table I below:
55 The split mold was then opened and each side of the
TABLE I specimen exposed to actinic radiation for 15 seconds.
Composition of Glass Fillers The total exposure time is one minute. After 10 minutes
Lithium Boro-Barium Barium post curing period, the strength of the material is mea
Aluminum Aluminum Aluminum sured in an Instron Universal Tester at a cross head
Silicate Silicate Silicate speed of 0.02 inches per minute.
60
Mol % Wt %. Mol % Wt 2 Mol % Wt % The crushing strengths varied according to the fol
SiO2 51 51.3 67 51.2 51 32.2 lowing order:
BaO O O 16.5 31.8 28.3 45.6
B2O3 O 0 10 8.7 0 0
Al2O3 20. 34.3 6.5 8.3 20.7 22.2 Barium- Boro-Barium- Lithium
Li2O 28.9 14.4 0 O 0 0
65 Aluminum Aluminum Aluminum Fused
Silicate Silicate Silicate Quartz
(32,000 psi) (25,500 psi) (25,000 psi) (6,800 psi)
A general method of preparing UV initiated compos
ites suitable for use in the present invention is as follows:
 5
4,192,795
6
Unpowdered quartz by itself has a high transmission TABLE II-continued
of UV radiation. However, due to the difference in Transmission Characteristics of Different Fillers
refractive index (UV region) or other factors, the pow Reference is Resin Mixture Film Having.11 mm. Thickness
dered quartz is not a preferred filler in this resin system, % Transmission at Different
The barium-aluminum-silicate on the other hand, ap Material and Wave Lengths in Nanometers
pears to have unique advantages as a filler in the UV Resin Mixture Thickness 300 325 350 375 400
initiated system in that it renders the resin system easy Quartz O O O O O
and quick to cure thereby resulting in a high strength Boro-barium
upon irradiation by UV light. Aluminum
This unique filler is particularly useful in filling mate O Silicate
Barium
O 2 4. 9 13.5
rials used in dentistry where deep cavities are to be Aluminum
restored quickly and completely. Silicate 22 92 72 45 34
The following examples further specifically define Maximum 95% transmission at 330mm
the present invention with respect to the method of
making a single paste product. The parts and percent 15
ages in the disclosure are by weight unless otherwise TABLE III
indicated. The examples below are intended to illustrate Transmission Characteristics of Different Fillers.
Reference Air
various preferred embodiments of this invention. % Transmission at Different
EXAMPLE 1. 20 Material and Thick - Wave Lengths in nanometers
Resin Mixture less 300 32s 350 375 400
A bulk solution is made by the general method out Lithium
lined above and consists of 21 gms of BisGMA resin, 3.5 Aluminum
gms of 1,6 hexane diacrylate, 0.003 gms of benzil and 2 Silicate 0.15 0.03 0 S 1.0 2.0 3.0
drops of trihexylamine. Four gms of this solution is Quartz O O O O O
separately treated with 2 gms of untreated lithium 25 Borobarium
aluminum
aluminum-silicate, 2 gms of untreated boro-barium silicate 3.5 4. 5 7 O
aluminum-silicate glass, 2 gms of untreated fused quartz Barium
and 2.7 gms untreated barium-aluminum-silicate. Be Aluminum
cause of its high density, barium-aluminum-silicate is Silicate O 49 47 34 27
used at a higher by weight percent to give equal volume 30 Maxiurnum 52% transmission at 335 mm.
loading for comparison with that of lithium-aluminum
silicate. The dental restorative materials are made in different
The mixture is stirred and kept in an oven at 120 F. shades ranging from Light, Light Grey, Yellow, Uni
for 30 minutes to remove the air. A few drops of this versal, Dark Yellow, etc. The colored composites are
solution is pressed against two glass slides so that a 35 made by incorporating different pigments, ususally the
continuous film is formed between the plates. The film oxides of metals. As the pigment concentrations are
is then cured by exposure to a spectroline B-100 lamp increased, the penetration of ultraviolet will be reduced.
for 15 minutes at a distance of 4 inches from the lamp. This loss in strength can be compensated by incorporat
The film was scraped off carefully and the transmission ing more barium-aluminum-silicate in the composite.
measured between 400 nm and 300 nm; the UV region EXAMPLE II
of the spectrum, in a Beckman DB-G double beam
grating spectrometer. The measurements are made with A composite is made and cured by the general
air as reference and the resin film without filler as refer method described above, using fused quartz as filler
ence. The results are tabulated in Tables II and III. The material. This composite exhibited a compressive
high transmission of film in which barium-aluminum 45 strength of 6,840 pounds per square inch (psi) on one
silicate was incorporated explains the higher strengths - minute exposure. When approximately 20% of the
of barium-aluminum-silicate incorporated composite quartz is replaced by barium-aluminum-silicate, the
material. strength increased to 22,000 psi. When barium
TABLE II aluminum-silicate is used alone, the strength increased
50 to 32,000 psi.
Transmission Characteristics of Different Fillers
Reference is Resin Mixture Film Having .11 mm Thickness The refractive indexes of all fillers used in this investi
% Transmission at Different gation were measured in powder form before silanation
Material and Wave Lengths in Nanometers by Fisher Scientific Wet Method. By this method, a
Resin Mixture Thickness 300 325 350 375 400 small amount of powder is mixed with liquids of known
Lithium 55 refractive index. if the opacity of the mix is minimum,
Aluminum the refractive index of the liquid is equal to that of the
Silicate 0.15 0.03 min 1.5 3 4 liquid. The values given in Table IV below are with
respect to Sodium line, 5893 A at 25° C.
TABLE IV
Refractive indexes, 5893 A at 25 C.
Refractive indexes of
reference liquids
Refractive indexes of liquid measured by measured by Bausch
Fisher Scientific Wet Method & Lomb Refractometer
Fiers:
Lithium-Aluminum
Silicate 1520 004 5197
Boro-Barium
 4,192,795
7
TABLE IV-continued
Refractive indexes, 5893 A at 25 C.
Refractive indexes of
reference liquids
Refractive indexes of liquid measured by measured by Bausch
Fisher Scientific Wet Method & Lomb Refractometer
Aluminum
Silicate 1540.004 1540
Barium-Aluminum
Silicate 576.004 15742
Fused Quartz 460.004 460
Refractive index of BisGMA resin 548
BisGMA resin + 1,6 hexanediacrylate 1.5340
(4.2 gm) (.7gm)
BisGMA resin -- 1,6 hexanediacrylate -- benzil 1.5340
(4.2 gm) (.7gm) (.02 gm)
BisGMA resin -- 16 hexanediacrylate - benzil -- trihexylamine 1.5322
(4.2 gm) (.7gm) (.2 gm) (.05 gm)

What is claimed is:

20 1. A U.V. curable dental restorative composition
In a strict sense the refractive indexes should be mea
sured at the maximum output of irradiating light which which consists essentially of a blend of BisGMA resin
is about 3,600 A. The refractive indexes of the resin and and about 50 to 85 weight percent of an inorganic filler
the other ingedients (except filler) successively added to material which includes a barium-aluminum-silicate
it in the same ratio as in composites were measured glass having the following composition in weight per
25 cent:
using Bausch & Lomb refractometer at 25°C. The val SiO2; 25-40%
ues are included in Table III. The difference between
two methods of estimation was checked by measuring BaO: 35-55%
the refractive index of reference liquids by the Bausch Al2O3: 15-30%.
& Lomb method and the results agree very closely. 2. A U.V. curable dental restorative composition
30 which consists essentially of the following composition:
The fused quartz has the least matching refractive
index with that of resin system and that is why the
composite filled with quartz has the least strength. If the
same reason extended to boro-barium-aluminum-silicate Parts by Weight
and barium-aluminum-silicate, the boro-barium 35 BisCMA 10-20
aluminum-silicate filled composite should have higher Diluent Monomer 2-5
strength and higher UV penetration than barium Benzil 00
aluminum-silicate. Obviously, other factors such a com Trihexylamine 0
Barium Aluminum Silicate Filier 70-85
position or crystal structure are influencing the promo
tion of the UV transmittance to a higher level. Barium 40
aluminum-silicate absorbs almost completely the x-ray in which the composition of the filler material consists
region of spectrum while it transmits a good portion of essentially of the following composition in weight per
ultraviolet rays which fall on it in the resin system. cent:
Other modifications and ramifications of the present SiO2: 25-40%
invention would appear to those skilled in the art upon BaO:35-55%
a reading of this disclosure. These are intended to be Al2O3: 15-30%.
included within the scope of this invention.

50

55

65