Note: Descriptions are shown in the official language in which they were submitted.
~;234~
1 7566-781
The present invention relates to resin-forming
composition suitable for medical or dental use, and more
particularly, to resin-forming composition applicable in
the field of bone and tooth which is extremely excellent in
physical properties, such as hardness, compressive strength,
abrasion resistance and so on, as well as ion bonding to the
hard tissue of the human body.
Among the material err medical or dental use, and
for dental use, in particular, the dental amalgam consisting
of silver alloy and mercury, and silicate cement have hitherto
been used as restorative filling material. The amalgam, however,
shows a low degree of marginary seal because of inferior impact
strength in addition
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.; ,
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to inferior bonding property to tooth, entailing the - -
fear of exerting unfavorable influences on the human .
body in the point of toxicity. further, the silicate
cement is readily soluble and entails such chortcom-
ins as tug be great in pulpal irritation in addition
to a low degree of bonding property to tooth and
inferior marginary goal.
hereupon, for anterior teeth developments
have been made of material consisting predominantly
of bi~phenol A diglycidyl methacryl2te (hereinafter
called ''BiC-GMA'' for short) and inorganic filler, such
as Hart (hereinafter called the Bis-GMl~ type come
posit resin), as new restorative filling material
substituting for conventional silicate cement (refer,
for instance, to the United States Patents 3,539~533;
3,066,112; 3,926~906, etc.), which has been improved
in such properties as compressive strength, water
resistance, pulpal irritation and so on as compared
to conventional material, such as slid silicate
cement, and widely used, but it is still far from
Satisfactory in the suspect of physical properties, Hugh
as hardness, compressive strength, abrasion resistance
and so on, or bonding to tooth and the like. in the
case of Bis-GMA it is in such a condition even in
anterior tooth, not to me~tiDn that it is next to
impossible to apply to molar which is more high in
occlusal pressure than anterior tooth.
With the Bis-G~lA type composite resin, for
reason that said physical functions are not enough
it can be said that Bis-GMA if insufficient in physical
properties a resin, being low in cross k and
that high viscosity of Bls-GMA, even if dolts were -
jointly used, restricts the amount of the inorganic
filler which is jointly used with the purpose of
improving physical properties of restorative-filling
material.
or reason that the Bis-GMA type composite
resin is scarce in the bonding property to tooth it
~23
-- 3 --
can be mentioned that because of joint use of a great
deal of inorganic filler in addition to somewhat scarce
bondability to tooth of Bis-GMA enhances the viscosity
of the composite resin resulting in no good nettability
on the tooth surface.
In order to improve various such shortcomings
with the BiC-GMA type composite resin attempts were
made to enhance the crocs-link of the resin and in-
crease the amount of inorganic filler in joint use by
using such low viscosity multi functional monomers a
trimethylolpropane trimethacrylste (hereinafter called
My for short) instead of sigma as disclosed in
British Patent No. 1,451,262, for instance, but in the
case of TEMPT bonding to tooth is hardly shown because
of its having no polar groups and viscosity of TUT
is too low which gives rise to such problems as lacking
in the surface curability as the composite resin and
settling of inorganic filler in paste condition.
In the cave, further, of TEMPT, pulpal if-
rotation by the residual monomer is very severe.
The instant inventor studied with the purpose of solving various said drawbacks with conventional
rental materiel, in consequence of which it was found
that by using resin-forming material consisting pro-
dominantly of the hereinafter-described acrylic monomer
of the specified structure there Gould be obtained
material or medical or dental use excellent in various
physical properties, ugh as hardness, compressive
strength, abrasion resistance and so on, weak in tissue
irritation and in addition, excellent in bonding to
the hard tissue of the human body.
he present invention is designed to provide
resin-forming material suitable for medical or dental
use which is excellent in various physical properties,
such as hardness, compressive strength, abrasion
resistance and so on, weak in the Tokyo irritation and
added to this extremely good in the bonding to the
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I
~Z3~Z'~
4 7566-7~1
hard tissue of the human body.
Another purpose of the present invention is to
provide resin-forming material suitable for medical or dental
use which is excellent in various said physical properties,
tissue irritation and bonding to the hard tissue and good in
operation in its practical use.
According to the present invention, there is
provided a composition of matter, especially useful as a
dental filling material, comprising:
from about 50 to about 95% by weight of finely
divided, inorganic filler other than inorganic nitrides, said
filler having a Oh's hardness of at least 5 and which filler
is safe and effective for use in a dental filling in the
human body, and
from about 50 to about 5% by weight of polymerizable
monomer component capable of polymerizing to form a binder
resin, wherein the monomer component consists essentially of
(1) from 60 to 100% by weight of a mixture
consisting of (a) from 30 to 95% by weight of first monomer
having the formula (II)
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O R
If 11
SHUCKS
I _ R2
WHOOSH f C 2 2 .... (II)
SUE SHEA
: O R3
and (b) from 5 to 70% by weight of second monomer having Formula
(III):
OR
till
SHUCKS
R4 1l 1 R 1 2
2 COUCH - f SCHICK - = OH .... (III)
SHUCKS
O R3
:
wherein Al, R2, R3 and R4 are the same or different, and
: are hydrogen, methyl, ethyl, m-popyl or isopropyl.
In the composition of the present invention the
compound represented by the formula (II) should be mixed in
proportions of 30 - 95~ by weight, preferably 40 - 80% by
weight and more preferably 45 - 70~ by weight and the compound
represented by the formula (III) in proportions of 5 - 70%
by weight, preferably 20 - 60% by weight and more preferably
30 - 55% by weight. Reasons:
: If the compound represented by the formula (II) is less
than 30% by weight, viz., the compound represented by the
formula ~III) is in excess of 70% by weight, in the case, in
particular, of using as dental filling material or restoratives
for crown bridge,
it 7
I
~23~
6 7566-781
the bonding to tooth and operation tends -to deteriorate.
In the instant invention those compounds of formulae
(II) and (III) wherein R1, R2, R3 and R4 are hydrogen or
methyl, in particular, are preferred. In this case, most
typically R1, R2 and R3 each in the formula (II) or R], R2, R3
and Reach in the formula (III) represent hydrogen or methyl.
Not only that, but those in which some of R1, R2, R3 and R4
represents hydrogen, and the others represents methyl, viz.,
mixed esters of acrylic acid and methacrylic acid, are also
preferred.
As typical examples of compounds represented
by the formula (II) are cited tetramethylolmethane triacrylate
and tetramethylolmethane trimethacrylate, for instance. As
typical examples of compounds represented by the formula (III)
are cited tetramethylolmethane tetraacryla-te and tetramethy~
lolme-thane -tetramethacrylate, for instance.
Conventionally, as already mentioned, i-t is known
to use triacrylate or trimethacrylate esters of
trimethylolpropane, but the compound of the said formula (II)
used in the present invention is characterized by possessing
another methylol group (-SHEA) besides the triacrylate or
trimethacrylate esters and the compound of the said formula
(III) is characterized in that it is a tetrafunctional acrylate
or methacrylate ester
~Z34~
7 7566~781
The compound of the said formula IT is excel-
lent in bonding to the hard tissue of the human body by
the effect with the methylol group and by using such compound
of the formula (II) and compound of the formula (III) in
combination, in particular, resin for medical or dental use
can be advantageously formed which is excellent in bonding
to the hard tissue of the human body as well as in the coup-
restive strength
The composite resin formed from the compounds of
lo formulae (II) and (III) has an extremely excellent water
resistance besides those characteristics mentioned just above
and shows very excellent operation on the occasion of its
practical use.
In addition, the compounds represented by the
formulae (II) and (III) can be used in combination with other
polymerizable monomers, such as conventionally known resin-
forming monomers err medical or dental use. In this case, the
amount of. the other monomers to be incorporated should be
40% by weight or less, preferably 30% by weight or less and
more preferably 20% by weight or less. In -the case where
monomers other than those of formulae (II) and (III) are con-
twined in an amount exceeding 50% by weight, they might lower
various excellent characteristics of the resin composition
.,;.
1;2342'~1
8 7566-7~1
of the present invention and it is not preferred. In this
connection, as typical examples of the polymerizable monomers
referred to here can be cited bismethacryloxyethoxydiphenyl-
propane, Bis-GMA, bisphenol A dimethacrylate, neopentylglycol
dimethacrylate and so forth.
The resin-forming composition of the present
invention, in its practical use, is usually used as a
composition in admixture of a catalyst for causing the
polymerization of the compound of the formula (II) and/or
compound of the formula (III) and an activator for
accelerating the formation of free radicals by the reaction
with such a catalyst.
Furthermore, the compounds of the formula (II)
and/or formula (III) is used in combination with any inorganic
fillers or medical or dental use which are nontoxic to the
human body with great hardness, such as powdered quartz,
powdered glass, glass beads, powdered aluminum oxide,
borosilicate glass, barium glass, hydroxy appetite and alumina
silicate, in addition to the catalyst and activator(~-SiO2,
Allah, Zr2 and ZrSiO4 are particularly preferred fillers.
these inorganic fillers, although it differs according to use,
should have Mows' scale of hardness of at least 5 and preferably
at least 6.
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~Z3~'Z~L
9 7566~781
The said inorganic filler should account for 50 - 95~ by
weight, preferably 50 - 90% by weight, and more preferably
70 - 90~ by weight, based on the total amount ox the resin-
forming composition.
If the inorganic filler is pretreated with a keying
agent, such a ~-methacryloxypropyl-trimethoxysilane,
vinyltriethoxysilane and so forth, the bond between the wormed
resin and the inorganic filler is intensified and physical
properties as material for medical or dental use is further
improved.
The monomers represented by the said formula (II) or
(III3 is readily polymerized and cured by means ox catalyst.
On this occasion, the application of heat often does harm the
human body when used in fields associated with the human body
and it is preferred to divide the monomers, into two, e.g. two
liquid forms, one containing the catalyst and the other
containing the activator, in such a manner as to be able to
cure the monomers at normal temperature when used and mix -the
both immediately prior -to use.
As the catalyst, a peroxide is preferred and it
should preferably be used in combination with the activator.
As the peroxide catalyst can be cited, for instance, dozily
peroxides, such as bouncily peroxide, parachlorobenzoyl peroxide,
2,4-dichlorobenzoyl peroxide, acutely peroxide, laurel peroxide
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~2;~2~
lo 7566-781
and so on, hydroperoxides, such as tertiary bottle hydra-
peroxide, cumin hydroperoxide, 2,5-dimethylhexane-
2,5-dihydroperoxide and so on, kitten peroxides, such
as methyl ethyl kitten peroxide and so on, proxy-
carbonates, such as tertiary bottle peroxybenzoate and
so on, etc.
These peroxide catalyst are preferably
used in proportions of Owl - 2.5% by weicJht based on the
total weight of the polymerizable monomers represented
lo by the formulae (II) and (III).
As the activator which may be used in combination
with the peroxide can be cited, for instance, tertiary amine,
such as N,N-bis-(2-hydroxyethyl)-4-methylaniline,
N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline,
N,N-bis-(2-hydroxyethyl)-3,5-dimethylaniline, N-methyl-
N-(2-hydroxyethyl)-4-methylaniline, 4-methylaniline,
N,N-dimethyl--p-toluidine, N,N-dimethylaniline, triethanolami.ne
and so on, and in addition, transition metal ions, such as
cobalt naphthenate, cobalt octana-te and so on, amine salts of
p-toluenesulphonic acids and sulphinic acids and so forth.
These activators can generally be used in
proportions of Owl to 2.5% by weicJht based on the total weicJht
of the polymeriæable monomers.
~23~
7566-78~
The monomers can also be polymerized and cured
by irradiation of ultraviolet rays. In this case, it is not
necessary to formulate into the two-liquid form and it is pro-
furred to use a photosensitizes in the amount of 0.1 - 10%
by weight based on the total weight of the polymerizable
monomers. As the photosensitizes can be cited, for instance,
carbonyl compounds, such as Bunsen, Bunsen methyl ether,
Bunsen ethyl ether, Austin, benzophenone, p-
chlorobenzophenone, p-methoxybenzophenone and so on,
Selfware compounds, such as tetramethylthiuranium moo-
sulfide, tetramethylthiuranium disulphide and so on,
issues
ago compounds, such as azobisi.sobutyronitrile, azobis-2,4-di.methylvalero-
nitrite and so on, peroxide compow1ds, such as bouncily peroxide, tertiary
bottle peroxide and so on, etc.
or the enhancement of preservability of the resin composition
it is effective to add an US absorber such as benzophenone type compound,
such as 2-hydroxy-4-methylbenzophenone, in the amount of 0.5-2.0 parts by
weight based on 100 punts by weight of the resin composition, or a stab-
liver generally called a free radical inhibitor, such as p-methoxyphenyl,
2,5-ditert.butyl-~-methylphenol and so on, in the amount of 0.05-0.20 part
by weight based on 100 parts by weight of the resin composition.
In a method of using such resin compositions, it is very con-
lenient to prepare in advance a paste-like substance paste A) comprising
an inorganic filler, resin composition and activator and a paste like sub-
stance (paste B) comprising an inorganic filler, resin composition and
catalyst, for instance, since the polymerization is initiated upon mixing
these -two pastes when used by doctors.
In the case of using such material in restoration of the hard
tissue of the human body, such us teeth and bones, the said material
possesses as such sufficient bonding to the hard tissue, but it is also
effective to apply the suit material after precutting the hard tissue with
a bonding agent, including ordinary bonding agents, such as 2-hydroxy-
ethylmethacrylate and so on, with the purpose of improviTIg the bonding to
the hard tissue. As the bonding agent, those described Jo European Patent
Application No. ~0101965.~l published under Publication No. 17937 on October
29, 1980, can also be used, which consist predominantly of a composition
comprising OWE by weight of polymeri.~able acrylate esters
., - .
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~239~2~
12 7566-781
and/or methacrylate esters having hydrophilic groups
comprising carboxyl, epoxy, amino or hydroxyl and
0.5 - 50% by weight of at least one member of organic
metal compound selected from the group consisting of
alkoxyl-containing titanium compounds and silicon compounds.
Thus, according to the present invention there
can be obtained resin compositions suitable for medical or
dental use which are extremely excellent in various physical
properties after curing, such as hardness, compressive strength,
abrasion resistance, little irritant to tissue and good in
bonding to the hard tissue of the human body and further,
very easy to handle in practical use.
Further, the resin-forming composition of the
present invention can be advantageously used not only as
material for bone cement and artificial bone in -the orthopedic
surgery and restorative surgery field but also as restorative
material for crown bridge, core material for crown, dental
cement, filling material, cavity lining material, root canal
filling material and so on, in the operative dentistry and
prosthetic dentistry field in particular.
The present invention will be specifically
explained with the reference to working examples as follows.
Unless otherwise specified, "part" and "%" in examples mean
"part by weight" and "% by weight''. Further, in examples the
composition of the resin-forming material (monomer) and filler
prior to curing
~234;~
- 13 - .
treatment is called the composite resin for short.
for conveniences sake. - . -
In this connection, in example the method for the preparation of composite resin and methods for
the measurement of compressive strength, abrasion,
water sorption, hardness, toothbrush abrasion, color-
in, linear thermal e~pancion coefficient, and tensile
strength follow the hereinafter-described procedures.
,, .
I A
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(1) A method for the preparation of composite resin:
-l. Preparation of filler
100 go. of powdery filler classified to particle
size of 50 microns or less was mixed to aqueous solution
obtained by vigorously mixing 10 g of r-methac~lox;y-
propyltrimethoxysilane and 1 ml of acetic acid with
agitation by addition of 200 ml of water and powdery
filler was separated after agitation. Powdery filler so
separated was dried in a hot air diver held at 105C for
24 hours whereby silane-treated filler was prepared.
In examples filler was all treated with Solon
and used.
-I. Preparation of monomer paste:
Monomer was divided into two equal parts, one
monomer was incorporated with polymerization activator
and filler prepared by following the procedure of -l
above (hereinafter called Paste A for short) and the
other monomer was incorporated with catalyst and filler
prepared by following the procedure of -l (hereinafter
called Paste B or short
In Examples, N~N-bis-(2~hydroxyethyl)-4-
methyl aniline was used as activator and bouncily peroxide
as catalyst.
or the mount in which the activator was mixed
to Paste A and the amount in which the catalyst was mixed
to Paste they were formulated in such a manner that
curing should occur about 3 minutes after mixing Paste A
and Paste I,
-I. Preparation of composite resin:
Paste A and Paste B were taken each in equal
amounts, mixed and kneaded together on kneading paper at
room temperature for 30 seconds whereby composite resin
was prepared
(2) Measurement of compressive strength:
Based on American Dental Association (ADA)
Specification No, 9 for Dental Silicate Cement compressive
strength was measured by the following procedures.
.,
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- 15 -
Composite resin was loaded in a mound, sealed
with sheeted glass, then placed in a pressure vessel and
left to stand under an atmosphere of 37C and relative
humidity of owe for 15 nuts The cured composite
resin was taken out from the mound and immersed in water
held at 37C for 24 hours whereby specimens were prepared.
By using Instron tester specimens were pressed at condo-
lions of press rate of 0.2 Mooney to determine their
compressive strength.
(3) Measurement of abrasion loss:
Cured composite resin loaded in and taken out
from the mound by following the procedures set forth in
section of "(2) Measurement of compressive strength" was
used as specimens for measurement of abrasion loss. the
specimens were dried in a hot air dryer held at 100C for
24 hours and then cooled in a desiccator for one hour and
weighed. The specimens were placed in a cylindrical metal
ball mill with an inner capacity of 500 ml and inner
diameter of 10 cm and simultaneously, 20 stainless steel
balls 1 mm across and 200 ml of polishing paste prepared
by adding 900 parts by weight of distilled water to 200
parts by weight of powdered Sweeney passing through a 325
mesh sieve as polishing material were loaded, sealed and
then rotated at a rate of 100 rum for 78 hours. After
I it was finished, the specimens were washed with water,
dried in the hot air dryer held at 100C for 24 hours and
cooled in the desiccator for another one hour and weighed.
Abrasion loss was calculated according to the following
equation:
Abrasion 108s (cm3)=((weight of unpolished specimens)
-(weight of polished specimens))/
(density of spew miens)
(4) Measurement of amount of water sorption:
Based on American Dental Association DADA)
Specification No. 27 for Direct willing Resins the amount
of water absorbed was measured by the following procedure.
Composite resin was cured to prepare a disk
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specimen 20 mm across and 1 mm thick. The specimen was
left to stand in a constant temperature dryer held at
37C, then placed in the desiccator, cooled for one hour
and weighed. Value when a constant quantity was reached
with repetition of this operation was set as dry weight.
Then, the specimen was immersed in water held at 37C for
7 days, then taken out, water on the surface was wiped off
with soft gauze and the specimen was weighed to determine
the weight of water absorbed. The amount of water
lo absorbed was calculated by the following equation:
Amount of water sorption weight after immersion)
(~g/cm2) -(conditioned weight))/
surface area of specimen
(5) Measurement of hardness: `
Measurement was made of Snoop hardness by means
of micro hardness tester of Shims make Composite resin
was cured to prepare a columnar specimen lo mm across and
5 mm high and a load of 900 g was carried on the flat
surface of the specimen for 15 minutes. The length of
dent formed on the surface of the specimen was measured
to determine Snoop hardness.
(6) Toothbrush abrasion test:
Composite resin was cured to prepare-and fix a
columnar specimen 13 mm across and 4 mm high. A come
I Marshall available toothbrush with a load of no g was
applied to the flat portion of the specimen and this
toothbrush way reciprocated at a stroke of 2 reciprocal
tions/second to polish the specimen surface. In the
meantime, solution prepared by diluting 150 g of come
I Marshall available toothpaste to l/2 with water was continuously added drops. After 8 hours the specimen
was washed with water, dried and weighed. Rate ox tooth-
brush abrasion loss was calcul2~ed by the following
equation
I Rate Of (weight of (weight of
toothbrush specimen - specimen
. before abrasion) after abrasion
aura soon = ,- n
weight of specimen before abrasion) x lvv
loss (%)
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~;23~Z~
_ 17-
(7) Coloring test:
Dusked test pieces 13 em across and 4 mm high
were surface-polishea with No. 800 emery paper and then
immersed in commercially available aqueous coffee solution
(solution obtained by dissolving 2.5 g of powdered coffee
in lo ml of water) at 37C for 4 days. the specimens were
washed with water, dried and then their color was measured
by means of calorimetry a product of Nippon Denshoku
~ogyo company, to read values I, a and b. likewise,
values I a and boy measured color values of the specimen
surfaces prior to immersing into the coffee solution were
read, the degree of discoloration YE was calculated by the
following equation and YE was set as a basis for coloring.
The greater the I, the greater is the degree of disk
coloration This test was also effected on the surface of the unpolished specimen
; = \/ Libya
(8) Measurement of linear thermal expansion coefficient:
Composite resin was enclosed in a glass tube 5 mm
in diameter and 20 mm in length, the opening of the tube
was sealed with cover glass for microscope, left to stand
at room temperature for 15 minutes and then cured composite
resin was taken out prom the glass tube whereby specimens
for measurement were prepared.
Measurement was made of the linear thermal
expansion coefficient of the specimens so prepared by
means of linear thermal expansion measuring instrument,
a product of Rucksack Dunk compare-. In making measurement
heating and temperature rising rate was set at 5C/min.
(9) Measurement of tensile strength:
Based on pressure tear test according to ADA
Specification No. 27 for the diametrical method tensile
strength was measured by the following procedure.
Composite resin was loaded in a stainless steel
mound 6 mm in inner diameter and 3 mm in height and the
opening of the mound was sealed with coyer lass for
1~3~2~
- 18 -
microscope. the mound was left to stand under an atmosphere
of 37C and relative humidity of 9~/0 for 15 minutes After
that, the cured composite resin was taken out from the
mound. this cured composite resin was polished by use of
powdered Six and then immersed in the water held at 37C
for 24 hours whereby specimens for measurement were pro-
pared.
Tensile strength of the specimens so prepared
was measured by means of Instron tension tester In making
measurement head press rate was set at l cm/min.
Example 1:
Silane-treated Shea was prepared following
the procedure for the preparation of filler in section
hen, using mixed monomer, as the monomer, pro-
pared by mixing tetramethylolmethane triacrylate (MOE)
and tetramethylolmethane tetracrylate (TMM-4~) in pro-
portions of 55:45 (by weight ratio). silane-treated
Shea, catalyst and activator, the mixed monomer was
divided into two equal parts for the preparation of Paste
Al-1 and Paste Bluely of following compositions according
to the procedure for the preparation of monomer paste
in section (1~-20
Paste Al-l and Paste Bluely so prepared were
taken each in equal amounts, mixed and Kneaded together
ox clouding paper at room temperature for 30 seconds
whereby composite resin was prepared.
his composite resin was loaded in a stainless
steel pipe with inner diameter of lo mm and height of 5 mm
at one end and excess part was removed off with sheeted
glass. An injection needle was stuck into the surface of
the composite resin at intervals of lo seconds at room
temperature to measure the curing time. It was about 3
minutes long.
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a lo Alp
~etramethylolmethane triacrylate TAO) 55
Tetramethylolmethane tetracrylate (TMM-4A) 45
Solon treated.~-SiO~ ox
5 N,N-bis-(2-hydroxyethyl)-4-methylanili~e . . Owe
Part by White
~e~ramethylolmethane triacrylate (TOM? 55
~etramethylolmethane tetracrylate (I PA) 45
Solon treated Shea 300
10 Bouncily peroxide 0.8
Compressive strength, abrasion loss and bonding
strength were measured of the composite resin and results
were shown in Table 1.
Paste Awls and Paste B's of oiling compositions
were formulated using various monomers conventionally
known as resin-forming material for medical or dental use
instead of the mixed monomer of TMM-3A and TMM-4A.
_ Put Allah _ Part Betty
Bisphenol A diglycidyl methacrylate (Bis-GMA) I
20 Triethyleneglycol dimethacrylate (T~GDMA) 20
Solon treated Shea 300
N,N-bis(2-hydroxyethyl)-4-methylaniline I
Part by weight
Bisphenol A diglycidyl methacrylate (Bis-GMA) 80
25 ~riethyleneglycol dimethacrylate (T~GDMA) 20
Solon treated Shea . ,~00
Bouncily peroxide 0~8
I; ED 'I I e i Fit
Bismethacryloxyetho~ydiphenylpro~ane (Bis-MEP~) 100
Solon treated Shea 300
~-bis(2-hydroxyethyl)-4-methylaniline 1.0
Paste By _ _ Part Betty
Bismethac~Jloxyethoxydiphenylpropane (Bis-MEPP) 100
Solon treated Asia . 300
Bouncily peroxide - 1.0
-'v-
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- SLY
_ 20 -
_ _ PAL _ Part by weight
Neopentylglycol dimethacrylate (NPGDMA) 100
Solon treated Asia zoo
N~N-bis(2-hydroxyethyl)-4-methylaniline 2.0
Paste Blue _ Part by weight
Neopentylglycol dimethacrylate ~I~PG-DMA) lo
Solon treated Asia 300
Bouncily peroxide 2.0
Paste Al-5 Part by weight
10 Trimethylolpropane triacrylate (TEMPT) lo
Solon treated Asia 300
l~N-bis(2-hydroxyethyl)-4-methylaniline 1.5
sty ~1-5 _ _ Part by weight
Trimethylolpropane triacrylate TEMPT lo
15 Solon treated Shea 3
Bouncily peroxide 1.5
These Paste As and Paste B's corresponding to
sub-numbers were taxed each in equal amounts and various
composite resins were prepared following the same pro-
seeders as the above. Compressive strengths, abrasion loss and bonding strengths were measured of these cured
composite resins. Results were shown in Table l:
."~ ,.. .
-- 21 --
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o h 13 l l O o 0 ED ted e +
_ _ __ I rl h 0 a) Ed
o O O O O Out Jo h I h p h
_ _ _ _ Jo a o o O h
Jo Jo h aye h
u En O O go O h Ed o 0
h N I N ON h 1 + 0 h
I _ Jo u
Do ¦ a 3 c e t ,
Jo A "I US
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Jo 1 by in Jo 13 . 0 c)
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It follows from the above table that the Cousteau
resin (Run No. 1) comprising the monomer composition of
- TMM-3A(55)/~MM-4A(45) belonging to the present irlvention
should be excellent in either of compressive strength,
abrasion loss and bonding strength as compared to the
composite resins of Run Nos. 2 - 5 comprising the monomer
compositions of ~is-GMA/~G, Bis-M~PP, ~PGDMA or TOT con-
ventionally known as the resin-forming monomer for medical
or dental use.
Bonding strength was measured by the following
procedure.
(1) Bonding strength to bovine dentin:
A fresh anterior bovine tooth implanted into a
square rod made of acryl resin was polished with emery
paper until the dentin exposed itself and further polished
and finished with No. 800 emery paper for the formation
of a contact surface whereby there was prepared a test-
piece of material for the bonding test with the bovine
dentin. This bonding test piece was stored in water.
Jo It was taken out from the water immediately before the
measurement was made The surface of the test piece was
well wiped off and further dried in a weak air stream.
Then, the bonding surface of the bovine dentin was coated
with composite resin and the square rod made of acryl
resin was stuck and pressed against the coated surface.
It was left to stand at room temperature for 15 minutes
and then immersed in the water held at 37C. for 24 hours.
Both ends of the acryl resin square rods of the specimen
were pulled apart at a rate of 1 mm/min. to determine the
bonding strength the bonding strength was indicated by
the maximum value and the minimum value of measured
numerical wheel measuring the respective specimens or
every 2,0 test pieces.
(2) Bonding strength to bovine enamel:
A fresh anterior bovine tooth implanted in a
square rod made of acryl resin was polished and leveled
with emery paper, and further polished and finished with
Jo
I
- 23 -
No. 800 emery paper for the formation of a bonding surface
whereby there was prepared a test piece of material for the
bonding test with the bovine enamel. this boding test piece
was stored in water. It was taken out from the water
immediately before the measurement was made. The surface
of the test piece was well wiped off and etched with 50%
aqueous phosphate solution for one minute It was success
lively washed with water and air dried using a weak air
stream Using the test piece of material for the bonding
test with the bovine enamel so prepared its bonding strength
way measured following the same procedure as in the case of
the measurement ox the bonding strength with the bovine
dentin and the measured values were indicated in the same
manner.
example 2:
Using, as the monomer, mixed monomers prepared
by mixing MOE and TMM-4A in various such proportions as
indicated in Table 2. Paste A 2 and Paste B 2 of following
compositions were prepared Paste A 2 and Paste B 2 were
mixed and kneaded together following the same procedure as
set forth in Example 1 whereby composite resins were
prepared D
Pate h Hart by weigh
-
MOE} 100 in total
Solon treated Asia - 300
N,N-bis(2-hydroxyethyl)-4-~ethylaniline -0~1
Pate B Part by weight
~MM-4~} 100 in total
Solon treated Asia 300
Bouncily peroxide 1~0
Compressive strength, abrasion loss amount of
water sorption and bonding to bovine tooth were measured of
these cured composite resins. Results were shown in Table
Jo h
.,. ~"~ .,
-- pa. -- .
. __ , _ _ _
R
1.
ho Lo It O O
El (i) Al I r J I Lo
us o R l l l l l l
or Lo If\ O O Lo Us C>
Jo Jo ,-1
m _ _
r
ox ED O O I I
O O
us to
O O O O O O O '
, __ _ _
'UI Lo Lo
h u o o o O o o o o
I: ¢ I
r a) _ _ _
Jo
En; VJ so I O 0
h I' Jo Lo Jo Jo
I I,
''
rod _ ___
I
':'~ _ __
rul O O O O ox
I - - - - - -
h ¢
l O O O O O O O
R O C` to I
__ _ ._ __ _
r-l Of to Jo Lo ED I
_ _ _ _
or '',
~.~;, 3
- 25 -
It is noted from the above table that either
triacrylate (TMM-3A) or tetracrylate ~TMM-4A) will suffice
for the monomer constituting the composite resin of the
present invention. The bonding strength value increases in
proportion to increased amount of TMM-~A mixed. or this
reason it is conceived that TMM_3A possesses another
methylol group (-CX20H) besides the triacrylate ester and
this methylol group contributes to the bonding with the
hard tissue of the human body.
In the case of the mixed monomer using a combine-
lion of TMM-zA and TMM-4A and the mixed monomer prepared
by miring them together in proportions of 30-70 parts by
weight of TMM_3A and 70-30 parts by weight of TMM-4A,
in particular dental composite resin could be advantageous-
lye formed which is excellent in the bonding with the hard
tissue of the human body with excellent compressive
strength.
In the case further, of using MOE and TMM-4A
in combination composite resin formed therefrom is found
to show very excellent water resistance besides the said
characteristics.
example 3:
Composite resins were prepared following the
same procedures of Example 1 except that there were used
US the mixed monomer of TMM_3A(55)/TMM AYE) belonging to
the present invention or conventionally known mixed
monomer of Bis-GMh(8o)/T~G(2o) as the resin-formi~g
monomer, given amounts of various inorganic metal oxides
conventionally known as the dental inorganic filler listed
Jo in Table 3 below as the Miller, catalyst and activator in
such amounts as set forth in the Table I. Comparative
strength and abrasion loss were measured of these cured
composite resins. Results were tabulated in Table 3.
_ 26 --
_ _ _
owe [I CO
to Jo 15~ Lo
h w OWE O O O O O
o
_ _ _
Jo
us JO O O O Q Q
US En C' O O O Jo
h \ Irk _ _ I O _
h Jo Jo to Tao
OWE I, `
O __ _
owe
UJr I O h
h\ I O O
We , , ,
h oh ~'~ I I I,
__ _ _
O
O O O ~^~ O 0
Jo Al h O Owe ¦ O
I to h
a pi
,-~ . _ _ _
Lo O Us O Lo
ox C' C' C' C` C' C'
I El
.~~ _ ___ __
Fly O O (U 0,
I (I C:) to I O Us
Jo h h I h
I lo
_ O N __ r;
O H _ _ \ _ _ O
I Lo I 0
Jo
Jo l Jo
X I: ill I.
_ _ Jo *
. _ I or ED
Jo ,
_, of
~23~Z~
_ 27 -
It is noted from the above table that if various
metal oxides conventionally known as dental inorganic
filler are to be used in combination with conventionally
known sigma type monomers, they will not be fully
satisfactory in the point of compressive strength and
abrasion resistance, whereas the monomer belonging to the
present invention, even if used in combination with these
metal oxides, will show fully satisfactory compressive
strength and abrasion resistance.
Example 4:
Using as the composite resin-forming monomer,
TMM-3~(55)/TMM-4A(45) or tetrame-thylolmethane trimeth-
acrylate (~MM-3M)(55)/tetramethylolmethane tetrameth-
acrylate (45) Paste A 4-l, B 4-l and Paste A 4-2 and
B 4-2 of following compositions were prepared. hollowing
the same procedure as that ox example l these pastes were
mixed for the preparation of composite resins.
Pate A 4-l _ Part by weight
TMM-~A 55
TAM PA 45
Solon treated Asia ~456
N7N-bis(2-hydroxyethyl)-4-met~ylaniline 0.8
Party weight
TMM-~A 55
TMM-4~ 45
Solon treated Asia? 456
Bouncily peroxide lo
Post 4-2_ _ Part by weight
Tetramethylolmethane trimethacrylate (TMM_~M) 55
Tetramethylolmethane tetramethacrylate (TMM-4M) 45
Solon treated Asia 456
N~-bis(?-hydroxyethyl)~4-methylaniline 0.8
Pa lo 4-? _ _ Part by weight
Tetramethylolmethane trimethacryiate (TMM-~!M) 55
Tetramethylolmethane tetramethacrylate (TMM_4M) 45
Solon treated Asia 456
Bouncily peroxide l 0
3~24~ -
_ I
Compressive strength abrasion loss and mount of
water sorption were measured of these cured composite resins.
results were tabulated in Table pa
-
Jo
- 29 -
_
I\ h I aye (I
0 I I Jo I
o o
Jo
I,
.- Jo
o o
~'0 O O
Jo
Us O O
Us C'
by I co
h ox
__
En
h
Jo _
~11 OX
_ ,_ ___
Al
Jo
I Us PA .
h Lo IS\
Jo
I
_ _
Jo .,
~23'~
_ 30 -
It follows from the above table that if TMM~3M
(55)/TMM-4M(45) is to be substituted for MOE)/
MOE) as the composite resin-formin~ monomer, dental
material obtained will have equally excellent physical
properties in the compressive strength, abrasion loss and
amount of water sorption. what is, it is noted there
that not only tetramethylolmethane in- or tetra-acrylate
but tetramethylolmethane in- or tetra-methacrylate should
also be preferred as the composite resin-forming monomer
of the present invention.
example 5:
Using, as the composite resin-forming monomer,
mixed monomers comprising a combination ox TMM-3A and
TMM-4A belonging to the present invention and conventionally
known dental resin-forming monomers Paste A 5-1, B 5-1 and
Paste A 5-2 and B 5-2 were prepared. hollowing the same
procedure as that of Example 1 these pastes were mixed
for the preparation ox composite resins.
_ _ Paste A 5-1 _ _ part by weight
'MOE 5
DMM-4A 3
~is-MEPP 13
NPGDMA
N,N'-bis(2-hydroxyethyl3-4-dimethylanilineloO
Solon treated Asia 456
, Paste By Part by weft
MOE 5
TMM-4A 33
BiS-MEPP 13
NPGDMA 7
Solon treated Asia 456
ensoul peroxide 1.2
Post 5-2 -Part by weight
TMM-4A 80
I Bis-GMA 10
NPGDMA 10
N~N-bis(2-hydrox~ethyl~-4-methylaniline 0~8
Solon treated Asia 456
,,
if 7566-781
Paste B 5-2 Part by Weight
-
TMM-4A 80
Bis-GMA 10
NPGDMA 10
Bouncily peroxide 1.0
Solon treated Sweeney 456
Compressive strength and abrasion loss were
measured of these cured composite resins and results were
tabulated in Table 5.
Table 5
. _ , _ _______ ___. . _, .
mount of Compressive Abrasion
Monomer composition tiler used strength loss
(Shea) (kg/cm2) (cm3)
TMM-3A(50)/TMM-4A(30)/
1 Bis-MEPP(13)/NPG(7)82 wit% 2,860 0.43
_
TMM-4A(80)/Bis-GMA(lQ)
, 2 NPG(10) if 2,840 0.41
.
It is noticed from the above t able that the cured
composite resins using mixed monomers prepared by mixing
about 20% by weight of conventionally known dental resin-
forming monomers, such as Bis-MEPP, NAG, Bis-GMA and so
on, to the composite reinforming monomer belonging to
the present invention should also be valuable as dental
material in terms of their physical property values.
They did not give rise to any compatibility problem.
. ,
I Jo
32 7566-781
Example 6:
TMM-3A/TMM-4A, the typical example of the present
invention, and conventionally known Bis-GMA/TEG, as the
composite resin-forming monomer and Sweeney of the present
invention, and conventionally known Shea, as the filler
were chosen and these monomers and fillers were combined
together for the preparation of 2 types each of pastes
Paste A 11-1 to A 11-2 and Paste B 11-1 to B 11-2 were
prepared.
Paste A 11 part by Weight
TMM-3A 55
TMM-4A 45
N,N-bis-(2-hydroxyethyl)-4-methylaniline 0.6,
Solon treated Shea 400
Paste B purity by Weight
-
TMM-3A 55
TMM-4A 45
swanks. peroxide 0.8
Solon treated Asia 400
Paste A purity by Weight
Bis-GMA 80
TEGDMA 20
N,N-bis-(2-hydroxyethyl)-4-methylaniline 0.6
Solon -treated -Sue 400
,
,. ,
I
I 7566-781
waste B 11-2 Part by Weight
Bis-GMA 80
TEGDMA 20
Bouncily peroxide 0.8
Solon treated Asia 400
Compressive strength, abrasion loss, toothbrush
abrasion loss, amount of water sorption, linear thermal
expansion coefficient, Snoop hardness, tensile strength,
coloring property and bonding strength were measured of
these various cured composite resins. Results were
tilted in Table 11(1) and Table 11(2).
Jo
:~23~24~
34 7566-781
r- ___ _ ,
I
D us O
Al I
I I I O ED O
I I
I X I'
I Jo
h o co I
a or
O h .
Jo O En o o
h O
.4 ,1 ox
O h us `- Jo I
En Q Al o o ,
C
Us o o
or
-- o o
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-1
Us o o
us IT En ox ED
a I_
,4 h so
O
__ ... .
O O o
h 3 Jo _
.__._ ox ox
Jo Jo Jo
I l
. _ 10 __ r-l
g O O
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En
O \ O
C 'n co u
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. N _
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3~2~
7566-7~3
. It --
a) on
O r-l Sue I
O O
I) Al
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. Al Jo
hut ,1 co
r-l I
_ C' ,0__ to
or
I Us 0 O O
I_ h I
,-~ a
Jo En
a) _. _ ___.... .
Jo on
I I
Jo
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._ .... - . _ ' Jo
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Us \ Lrl O
or
O Us O
U i V
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_ Jo
_________~_____ _ I
of .,
~23~Z4~
36 7566-78~.
It follows from the above table that the composite
resins according to the present invention (Run No. 1), as
compared with the composite resin (Run No. 2) prepared by
combining together the conventionally known composite resin-
forming monomer and filler, have such characteristic features
as to be less in the linear thermal expansion coefficient
as well as in the amount of water adsorption, toothbrush
abrasion loss and discoloration or the like, besides markedly
excellent mechanical strengths, such as compressive strength,
abrasion resistance, Snoop hardness, tensile strength and
so on, and markedly excellent bonding to the hard tissue of
the human body, and can be advantageously used as medical or
dental material.
: In the above table, the column as to the bonding
strength to the bovine enamel (1) indicates the bonding strength
when the composite resin is applied as such to the bovine enamel
and the column as to the bonding strength to bovine enamel (2)
indicates bonding strength to the bovine enamel surface which
is coated with a mixture of equal amounts of bonding agents
A and B of compositions shown below and set forth in European
Patent Application No. 80101965.4 published under Publication
No. 17937 on October 29, 1980, followed by application of the
composite resin. It is no-ted from a comparison ox bonding
strengths with the bovine enamel I and (2) of Run No. 2
I
37 7566-781
that it is very effective in the point of bondability when the
composite resin is applied after precutting the hard tissue
of the human body with the bonding agent.
Bonding agent A Part by Weight
TMM-3A 98
Tetraisopropyltitanate 2
N,N-bis-(2-hydroxyethyl)-4-methylaniline 2
Bonding agent B Part by Weight
TMM-3A 98
Tetraisopropyltitanate 2
Bunnell peroxide 2
Detroit. butyl~4-methylphenol 0.15
Example 7:
Paste A 11-1 and Paste B 11-1 mentioned in Example 6
were mixed in equal amounts for the preparation of composite
resins of Run No. 1 in the following Tale 6. By using them
cytotoxicity tests by tissue culture were conducted.
The composite resin was enclosed in a glass tube
with a surface area of 28.3 mm2~ the specimen immediately
after curing was immersed in 5 ml of culture medium (199) and
rotated at a rate of 200 rum at 37C for 24 hours and then
1 ml of the medium was interacted with L-cells ~2.8 x 104) to
count cell numbers after days and after 4 days. Results were
shown in Table 6.
~2~34~
38 7566-781
Likewise, cytotoxity tests were conducted on -the
composite resin comprising Paste A 1-2 and Paste s 1-2 of
Example 1 and results were also tabulated in Table 6.
Table 6
_ , Filler in 1 ml
Monomer composition Kind Amount After After
(wit I) 2 days 4 days
Blank I 6x104 56x104
1 TMM-3A(55)/TMM-4A(95) Asia 80 3.2x104 22x104
I Bis-GMA(80)/TEGDMA(20) 75 2.3x
* indicated Control.
As clear from the above table, the composite resin
of the present invention is less in the action of inhibiting
the cell multiplication as compared to the conventional type
of composite resin.
Example 8:
Clinical observations were conducted by the
following procedure.
Caries of a patient was removed by a dental drill and it was
cleansed with water and the enamel of the caries was immedi-
lately coated by a brush with 40~ phosphate etching solution.
After one minute it was cleansed with water and further
dried in an air stream for the formation of a clean enamel
surface.
I
3~2~L~
39 7566~781
Then, the enamel surface in the cavity including
this surface was thinly coated by sponge cotton with a
mixture of equal amounts of bonding agents A and B mentioned
in Example 6. Respectively different composite resins
were applied to the caries in molars and in anterior teeth.
That is, the composite resin prepared by mixing Paste A 11-1
and Paste B 11-1 mentioned in Example 6 with powdered Asia
incorporated as the filler was applied to anterior teeth. The
composite resin prepared by mixing and kneading together these
Paste A and Paste B in equal amounts was immediately enclosed
in the cavity and simultaneously, the filled portion was
pressed and held on with celluloid strips for 5 minutes whereby
the composite resin was cured. After it was cured, the
celluloid strips were removed, the form was put in order by
the dental drill and treatment was finished.
The following are results of these clinical
observations.
(1) Results of application to anterior teeth:
Class 3 and Class 5 cavities, in particular, were
filled. There were 129 clinical cases. Conventionally
anterior teeth were being filled with dental composite
I
_ 40 -
resins. these existing dental composite resins however
are weak in mechanical strengths, such as compressive
strength, abrasion resistance and so on, and low in bond-
it strength and hence, indications were made of various
problems, such as incidence of recurrent caries on the
contact surface between the restorative filling material
and the tooth with -the lapse of time after the filling,
discoloration and surface abrasion arising from biting,
brush polishing and so forth.
the composite resin of the present invention,
even with the lapse of sic (6) months' time after its
filling, was almost free from such problems as indicated o
of the existing dental composite resin. the composite
resin of the present invention was set free from recurrent
caries in the interface with the tooth because of the resin
having high bonding strength to the tooth and high abrasion
resistance Not only that, but hardly any discoloration
was observed
these results of clinical observations show -that
the composite resin comprising a combination of the combo-
site resin-forming monomer belonging to the present invent
lion and the existing metal oxide powdery filler should be
markedly excellent in the performances when applying as
the anterior tooth restorative filling material a compared
to the existing dental composite resin.
"'l,'
