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    • 专利摘要:
    Compsn. comprises (a) prepolymer with >=2 ethylenic unsatd. gps., formed by reacting a urethane prepolymer with an ethylenic unsatd. monomer and (b) a filler contng. >=50 wt. % of particles not >100 mu. A catalyst is also used which is either a mixt. of peroxide and accelerator or a photosensitive catalyst. The filler is pref. borosilicate glass and the monomer is e.g. CH2=C(R3)-COOH where R is H or hydrocarbyl.
    公开号:SU799629A3
    申请号:SU742025932
    申请日:1974-04-24
    公开日:1981-01-23
    发明作者:Бэрнетт Кэнтвелл Джон；Эдвард Бенет Джонс Майкл；Томас Айюан；Родни Трейнор Джеймс；Франтишек Яворжин Джозеф；Немчек Иозеф
    申请人:Империал Кемикал Индастриз Лими-Тед (Фирма)；
    IPC主号:
    专利说明:

    (54) COMPOSITION FOR SEALING TEETH end groups and therefore, in order to obtain a true swine agent, his last is subjected to reaction with oxyalkyl acrylate or methacrylate. The urethane prepolymer has a linear, unbranched structure, which can be achieved by reacting di-isocyanate and a difunctional compound such as a diol and dicarboxylic acid. A urethane prepolymer that is linear and may contain isocyanate end groups and is obtained by reacting a diol with a diisocyanate to yield a urethane prepolymer having the structure PCN- {Z-N4-COO-Tl 0-OC-NH) ,. (1) where the diisocyanate has the structure OCN - R, -NCO, and the diol has the structure HO-R (with R and R being a bivalent hydrocarbon group, n is an integer. The reaction of the urethane prepolymer with oxyacrylate or methacrylate gives the polymerization prepolymer having the structure CH -0-; 4-NH-fR-MH-CO-0 - R2 0-OC-NH) - TZ-NH-X-C where X is defined below and R is a hydrogen or hydrocarbon group so that the urethane polymer can have isocyanate end groups; when preparing the polymer, there must be a molar excess of diisocyanate over diol, since the value of n in the polymer depends on m the ratio of diisocyanate to diol, and it decreases with an increase in this ratio. The formation of the isocyanate-terminal prepolymer can be accelerated by using a catalyst, for example, tertiary amines and methane salts, i.e., tin octaate and, in particular, dibutyl tin dilaurate. . By reacting a diol and a diisocyanate, a viscous Urethane photo-polymer can be obtained. When n is a large number, the polymer may be solid, and therefore the diol is reacted with a diisodianate in the presence of an inert diluent. Similarly, when the urethane polymer is very viscous or solid, the reaction of the last prepolymer and the ethylenically saturated monomer containing the uranium reactive groups to form the polymerizing prepolymer is carried out in the presence of an inert solvent. The diluent must be completely free of groups that can react with isocyanate groups, at least to the extent that the diluent does not interfere with polymer formation. This may be a liquid-ethylenically unsaturated monomer copolymerized with a prepolymer. When a polymerizable formolymer having a structure (GI) is obtained in an inert diluent, the polymer can be separated from the diluent by evaporation or by adding a solvent that does not dissolve the prepolymer to the latter. In order for the filling obtained by the hardening of the filling composition to have increased strength, modulus of elasticity and elevation; m spreading resistance, the urethane prepolymer is formed from a polyisocyanate and a polyfunctional compound, at least one of which, and preferably both of them, would contain one cyclic (aromatic) group in the chain between the isocyanate-reactive groups in the polyfunctional compound or between the isocyanate groups in polyisocyanate, respectively. Thus, the urethane prepolymer is formed from a diol and a diisocyanate having, respectively, the structure and OCN-R -NCO, where one of the divalent hydrocarbon radicals R and Rj has an internal (aromatic) cyclic group. Achievement of high strength, F4ODULA of elasticity and resistance to the spread of the filling, the polymerizing prepolymer has the structure (it), where R and Rg,, .Rj and X have the described values, n is an integer from 1 to 20. One of the groups RJ, Rj contains at least one cyclic group in the polymer chain, no more than 30 atoms at all, and when increased strength is needed no more than 20 and, preferably, no more than 12 atoms in the chain between adjacent cyclic groups. In the case when n is 1 and only R contains one cyclic group, there must be from 12 to 30 atoms in the chain between the cyclic group in P., nitrogen attached to group X. To obtain a urethane prepolymer and, therefore, a polymerizable prepolymer, n in the urethane prepolymer should be no more than 10 or not more than 5. Thus, the molar ratio of isocyanate groups in the diisocyanate or their mixtures to hydroxyl groups in the diol or their mixture from which the polymer with the isocyanate is obtained at the ends should be 1, 1: 1 or 1.2: 1. The value of p in urethane prepolyme F e is not more than 3, and the molar ratio of isocyanate groups in diisocyanate or their mixtures to hydroxyl groups in diol, or their mixture, from which the urethane prepolymer is obtained, must be 1.33: 1 or more. Examples of diols containing cyclic groups that can be used in the preparation of a urethane prepolymer include, for example, cycloalkane diols 1: 3 and 1: 4 — cyclohexane diol and a diol having a structure. In this case, the Rg group in the urethane prepolymer has a structure, respectively. , 0 Other suitable diols include cycloalkane dialkanols, for example cyclohexane dimethanol or cyclohexane diethanol, polycycloalkane dialkanol aryl dialkanol and condensates of alkylene oxides with aromatic compounds containing two fnol groups. To achieve the above properties of the fillings, diols with the structural formula HO-f CH-CM-0-) Vt ° are required with a compound having the structure HO-Ar -OH, preferably Examples of diols that do not have cyclic groups in the chain include ethylene glycol and propylene glycol. In that case, R; has the structure -CHj -CH or -CH (j-CH-CHj-, butylene glycol, diethylene glycol and its derivatives, in which one or more carbon atoms are replaced by an atom or groups that do not react with hydroxyl and isocyanate groups. Diisocyanates containing cyclic groups, which can be used for the preparation of the polymer include Diisocyanates, in which the chain between intrinsic valences has at least one aromatic group or one cycloaromatic group or in which the chain of me: with free valences includes a combination one aromatic and one cycloaliphatic groups. Cycloaliphatic Diisocyanates include Diisocyanates with the structure of VV.
    which are oxyalkylated derivatives of phenolic compounds, where Ri and Rg are hydrogen atoms or hydroxy groups, for example methyl, and Ap is a divalent aromatic group.
    In this case, the divalent group K has the structure
    f CH-GH-OtaV- (O-CH-CH,
    4 b
    R.
    Here, An may be a monodrome, for example, as in phenylene, combined polydermal, as in naphthalene or anthra-price, has the structural formula
    where Y is a bivalent bond, for example -0-, 50g, CO-, or CH, or a substituted -CH derivative. , eg
    CH - IS-7) 1 3
    If one of the groups Rd and Rg is hydrogen, and the other is methyl,
    H or both r,
    hydrogen, diol mozhi
    but obtained by the reaction of propylene oxide or ethylene oxide with phenolic
    where Y is a two-valent bond, which can be, for example, -CH2- or its substituted derivatives, -0-,
    5 50g2, -CO- and isocyanate group are attached in para- or meta-position to group V. (4,4-dicyclohexylmethane diisocyanate).
    Aromatic Diisocyanates that can be used include, for example, 2: 4 - or 2: 6 - toluene Diisocyanates, or mixtures of them, in this case the divalent group K, have the structure
    45
    or
    or a combination of these structures.
    Other suitable aromatic diisocyanates have the structure OCN - (CH5.) T- (CH5) t -NCO, where M is an integer, is arranged in such a way that there are no more than 30 atoms between the cyclic groups in the urethane prepolymer obtained from them, t. is. xylene diisocyanate.
    A particularly suitable aromatic diisocyanate has the structure
    NCO
    Wasps
    V. /
    where Y is a divalent bond, which is 5 ramo). the set has the previously described values, and where the isocyanate group is attached in the meta or para position to the group V (4,4-di-eocyanatipiphenyl methane).  Di-isocyanates that do not contain cyclic groups can be used to make a urethane prepolymer.  Such suitable diisocyanates include, for example, tetramethylene diisocyanate, pentamethylene diisocyanate and hexamethylene diisocyanate, in which case the divalent group R has the structure (. -Cou g-n-rn-Cc-u. ,) The ethylene-saturated monomer, which reacts with the urethane prepolymer to form the prepolymer polymerized, has an isocyanate group.  The ethylenically unsaturated monomer that reacts with the urethane prepolymer to produce the polymerized dvigos prepolymer is oxyalkyl acrylate or methacrylate, and it has the structure of an HF – COOH OH p-OH where Rrj is hydrogen or methyl; p is an integer of at least 2, or derivatives of the indicated monomer, in which one or more hydrogen atoms in the group - (CHfj) - are replaced by a hydrocarbon group, for example alkyl.  e.  methyl.  In this case, the group —X— in the polymerizing prepolymer (II) has the structure —COO- (CHO) p-0 — CO—. Suitable examples include hydroxyethyl or hydroxypropyl acrylate or methacrylate obtained by the reaction of acrylic acid or methacryloic acid. with ethylene oxide or propylene oxide, in this case, group X in a polymer-cement polymer (I has the structure -OOO-CQU-OH VD-OO, f.  where, respectively, both K. .  and R-at is hydrogen, and one of R,, R is hydrogen, the other is methyl.  When the filler is in the form of a ball, at least 5 balls should have a diameter of not more than 1000 microns.  When the filler is at least 50 filaments should be no more than 1000 microns long.  It is necessary that all particles of the filler have a maximum size of not more than 1000 microns.  Mixing the filler with the polymerisation with the prepolymer usually becomes easier with decreasing particle size of the filler.  The preferred maximum size of the filler particles is determined by its shape.  Thus, the filler is in the form of filaments, the maximum size of filaments should be no more than 100-500 microns.  When the filler is in the form of a ball, plates or irregularly molded, its maximum particle size should be no more than 300 microns, or in the region of 1-100 microns.  In order to obtain a solid dental pl-ombu upon solidification of the composition, it is necessary that the filler particles have a hardness of 100.  The greater the hardness of the filler particles in the composition, the greater the hardness of the dental fillings obtained during solidification of the composition, and for this reason it is necessary that the hardness of the filler is 300 or 500.  In order for the dental filling obtained when the dental composition of a complete composition to hardened does not differ in appearance from the natural tooth, it is desirable to use a translucent filler.  Dental filling composition should contain from 60 to 90 weight. % filler to ensure that the dental fill obtained during the hardening of the composition has the necessary resistance to abrasion, hardness, low shrinkage during hardening and a low coefficient of thermal expansion.  Mixtures of various fillers may be used.  The filler may be in the form of laapa, plates, threads, panicles, or may be unevenly molded.  A suitable filler is, for example, apatite, sodium glass, quartz, silica gel, borosilicate glass, synthetic sapphire (aluminum) or metallic yarns.  Mixing the polymerization of the prepolymer with a filler to form a tooth-filling compound can be achieved by mixing the prepolymer and the filler together.  However, since the polymerizing prepolymer, especially with the copolymerizable monomer, can be viscous and therefore difficult to interchange with the filler, in order to achieve uniform mixing of the polymerizing prepolymer, especially with the polymerization monomer, it can be diluted with a suitable diluent to reduce the viscosity and thus achieve more easily uniform mixing with the filler.  After laugh. nor is the diluent removed by evaporation.  The diluent may be a copolymeriscchimes ethylenically unsaturated monomer, and the monomer, if necessary, is completely removed after the mixing is achieved, or in the case that the dental filling of the filling composition has a copolymerizable ethylenically unsaturated monomer.  The content of the monomer is then reduced to the desired degree.  In order to obtain a dental filling, in which the filler is well adhered to the solidified polymerizing prepolymer, the filler must be treated with a binding agent that can react with both the filler and the polymerizing prepolymer before smearing the filler and the polymerizing prepolymer.  The binding agent increases the attraction force between the interfacial agent and the solidified polymerizing prepolymer in the seal.  Suitable binding agents for use with glass include, for example, methacryloxypropyl trimethoxysilane, α-aminopropyl tri ethoxysilane and / -glycidoxypropyltrimethoxysilane.  the tooth-filling composition may contain a liquid ethylenically unsaturated monomer copolymerizable with a polymerizing prepolymer, and must contain such a monomer when the polymerizing prepolymer is solid in order for the dental filling composition to be liquid and have a plastic consistency.   The amount of such an ethylenically unsaturated monomer should be such as to ensure only the necessary liquid state of the composition, and lies in the range of 32.5 - 43.8% by weight of the composition.  Suitable liquid copolymerizable ethylenically unsaturated monomers, the polymers of which are water-soluble, include vinyl monomers, such as vinyl esters, and acrylic and methacrylic acids.  Monomers should not be toxic.  Suitable vinyl esters include vinyl acetate, acrylic acid esters having the formula CHj CH-COO where Rjj is alkyl, aryl, alkaryl, aral kil. or cycloalkyl group.  For example, R may be an alkyl group, having from 1 to 20, preferably 1 to 10, carbon atoms.  Specific vinyl ethers that can be listed include methyl methacrylate, ethyl methacrylate, n-iso-propylmethacrylate, and n-iso- and tertiary-butylmethacrylate.  Other suitable vinyl esters include esters of the formula CH, (COOR), where R7.  may be alkyl, for example methyl, in the ether with the formula (COOOR), R and R may be the same or different.  Specific vinyl ethers include methyl methacrylate, ethyl methacrylate, p iso-propyl methacrylate, and p iso- and tratium-butyl methacrylate.  Mixtures of acids and esters should be used.  Can also be used 1 semi-functional vinyl monomers, t.  e.  monomers containing two or more vinyl groups.  Suitable monomers. include glycol dimethacrylate, diallyl phthalate and triallyl cyanurate.  The composition is drained into the desired shape and then cured to form a solid filling by polymerizing the polymerizing prepolymer, if necessary, together with the ethylenically unsaturated monomer copolymerizable with it.  The curing of the composition with obtaining dental fillings can be made with a catalyst.  It is desirable for the catalyst to do this at a relatively low temperature, close to the ambient temperature, since the use of elevated temperatures is undesirable for the patient.  A suitable catalyst that promotes curing at relatively low temperatures includes a mixture of peroxide and accelerator, for example, peroxide and amine, or a mixture of benzoyl peroxide and N, N-dimethyl-toluidone. Other catalysts include a mixture of peroxide and cobalt accelerator, for example, a mixture of methyl ethyl ketone and octoate and octoate and a mixture of methyl ethyl ketone and octoate and a mixture of methyl ethyl ketone and octoate and a cobalt accelerator, for example, a mixture of methyl ethyl ketone and octoate and a mixture of peroxide and cobalt accelerator, for example, a mixture of methyl ethyl ketone and octoate and a mixture of peroxide and cobalt accelerator, for example , cobalt naphthenate or cobalt naphthenate and dimethylaniline.  Catalyst operating at relatively low temperatures must be mixed quickly before use.  The amount of catalyst used is 0.5–6% by weight of the composition.  A tooth-filling compound containing a photosensitive catalyst may harden when irradiated with ultraviolet radiation, such as radiation, having a wavelength in the range of about 230-240 microns.  The composition can also harden when exposed to visible radiation and especially visible radiation, having a wavelength in the region of 400-500 microns.  The photosensitive substance may be present in the dental composition in a concentration of 0.01-5% by weight of the polymerizing material in the composition, although other concentrations may be used.  Preferably, the photoactive substance is present at a concentration of 0.5-5% by weight of the composition polymerizing material.  The reducing agent present in the sensitive catalyst must be able to reduce the photosensitive material when it is in the excited state.  The reducing agent must have a slight inhibitory effect on polymerization. Suitable reducing agents include compounds having the structure of ft-MR, where I is an element of group Vj, the periodic system, and R, which f4oryT are the same or different, are hydrogen atoms, hydrocarbon groups, substituted hydrocarbon groups, or groups in which the two R together with the element M form a closed ring system, and no more than two compounds R are hydrogen atoms, and the element M is attached indirectly to the apo aticheskoy group element M in the reducing - phosphorus, antimony or nitrogen.  The reducing agent may be primary, secondary or tertiary, so that in the structure two, one or none of the compounds R, respectively, may be hydrogen atoms.  For example, the reducing agent may be a primary, secondary, or tertiary amine or phosphine.  One or more of the groups may be hydrocarbons.  The hydrocarbon group may be alkyl, cycloalkyl or aralkyl.  Thus, the R group may be an alkyl group having 1-10 carbon atoms.  Examples of suitable reducing agents in which one or more of the R- groups are a hydrocarbon include propylamine, butylamine, pentylamine, diphythylamine, diphythylamine, trimethylamine, triethylamine, triphylamine, tributylamine, triptylamine, trimethylamine; may be substituted hydrocarbon groups and, in particular, a hydrocarbon group may have a substituent having the structure RI -, where M is E1, T of group Vj of the periodic system, and R - alkylen chain and Rr, which may be identical or different, are atoms of water or genus. hydrocarbon groups.  Examples of a reducing agent having the structure R- (, in which, at the edge, one of the groups R is substituted by a hydrocarbon group, include diamines with the structure (where n is an integer of at least two.  The R | j groups, which may be the same or different, are hydrogen atoms or uranium carbon.  For example, a reducing agent can be ethylenediamine, trimethylene. diamine tetramethylenediamine, pentamethylenediamine or hexamethylenediamine, N-hydrocarbon, or N-al yl derivatives of them.  Other approaches, including reducing agents, have the structure 4N- (CH2), - Nr where one or more hydrogen atoms in the -CH group have an -N group, especially the NH group.   Examples of a reducing agent, where the element M forms part of a closed ring system, include piperidine and N-hydrocarbon, especially L-alkyl, derivatives of piperidine.  Other reducing agents include triallylamine, (allyl) N UZ- (giglyl) / 2, allyl thiourea, and soluble salts of aromatic sulfinic acids.  Preferably, the reducing agent is present in a concentration of 1-5% by weight of the dental composition to be polymerized.  Example 1  Obtaining a mixture of vinylurethane and methyl methacrylate :.  352 weight. h  the condensate obtained by the reaction of 2: 2 -bis (-p-hydroxyphenyl) propane and propylene oxide in a molar ratio of 1: 2 is heated to melt the condensate and stirred under reduced pressure to degas the condensate.  500 weight. h  4: 4 -diisocyanatodiphenyl methane is heated, mixed and degassed separately.  The condensate and diisocyanate (in a molar ratio of diisocyanate to condensate 2: 1) are then mixed together and 556 hours of methyl methacrylate, which has been previously dried over calcium hydride, are added to the mixture, and then 0.14 hours.  dibutyl tin of nilauret.  The mixture is cooled in an ice bath with the control of the exotherm, obtained during the reaction to form the urethane prepolymer, so that the temperature does not rise higher.  Stirring is continued for 1-1 / 2 hours after termination of the heat.  260 h, 2- (hydroxyethyl) methacryl, which is preliminarily distilled and degassed, the resulting mixture is stirred for about one and a half hours in order to prepare a mixture of ethylenically unsaturated polymerization and despolymer, t. e.  vinylurethane and methyl methacrylate containing 1112 hours.  vinylurethane and 556 h of methyl methacrylate, tons  e.  in the ratio of 2: 1.  The preparation of the composition for sealing teeth.  60 h, a mixture of polymerizable prepolymer and methyl methacrylate, obtained earlier, is mixed with 180 weight. h  glass balls, with 80 weight. % of these balls have a diameter of 4-44 microns.  The mixture is then stirred, methyl methacrylate is added to the mixture, 6 h.  catalyst solution formed by dissolving 2 h. benzyl in 4 dimethylaminoethyl methacrylate and 4 4 methyl methacrylate.  After stirring for 15 minutes, the pressure is reduced, and methyl methacrylate, which is added with additional stirring, is removed by evaporation.  The composition consists of pastes of different material for filling the beads in the following ratio of weight, weight. %: Filler73.3 Polymerizable material 26.7 The polymerizable material has the composition,%: Polymerizable prepolymer 60.5 Methyl methacrylate 34.0 Catalyst5-, 5 The paste-like mixture is then placed in a cylindrical glass form and irradiated with a blue lamp for 15 minutes to solidify the mixture.  Hardened material has the following properties: Compressive strength, N mm 178 Compression module, N mm-3690 RockwefC hardness, H171 scale Bending module, mm-14500 Water adsorption (after 66 days of incubation in water at 37 °), weight. % 0,75 PRI me R 2.  Carried out as in Example 1, except for 30 hours, mixtures of ethylenically unsaturated polymerized prepolymer and methyl methacrylate, and 3 hours.  of a catcher, and instead of glass beads, 60 glass fibers are used, with sizes of 10-200 microns.  Before mixing with other components, the composition of the surface of the glass strands is coated with methacryloxypropyltrimethoxysil by adding 100 hours.  glass filaments, which are preheated from 400 s and cooled in a desiccator, to a solution of 1 h.  Oj is a hydroxypropyltrimethoxysilane sorbent per 100 h of methanol, evaporation of methanol, and sieve the threads through a sieve.  62 microns and the final heating strands to.  1400s for curing the silane.  The composition is a paste-like material for tooth filling, with the following ratio of components,%: Filler64.5 Polymerizable material35.5 The polymerizable material has become,%: Polymerizable prepolymer 60.5 Methyl methacrylate 34.0 Catalyst5.5 The hardened material has the following properties: Compressive strength, N 201 Compressor module, N mm- 3540 RO hardness, с B82 scale Rockwe EV hardness, H scale 168 Abrasion resistance, MK. bIM Example 3.  Carry out according to Priru 1, with the exception that 15 hours are taken.  a mixture of ethylenically unsaturated polymerizable prepolymer of methyl methacrylate and 1.5 hours, catalysis, and 36 hours of use instead of glass beads.  silica powder, the coating of which is coated with α-metalloxypropyltrimethoxysilane in accordance with the procedure described by Reamer 2.  The composition is a pastas material for sealing s, with the ratio of components,%: Filler. 68.5 Polymerize | 1st material31.5 The polymerized material has a blowing composition,%: Polymerizable prepolymer 60.5 Methyl methacrylate 34.0 Catalyst5.5 The hardened material has the following properties: Compressive strength, N mm 157, 6 Compressor module, N mm ЗГ50 Hardness according to Rockwe IT, Scale 81 la B Rockwe ft hardness / scale170 0.007 la N Resistance to abrasion, MKMM Coefficient of linear thermal expansion, ppm at 40 ° Example 4.  Getting Vinylure  500 g of freshly distilled 4.4 isocyanatodiphenylmethane is washed with ml of methylene chloride in a 5-liter flask which is pre-purged with nitrogen. .  The flask is then equipped with a glass core stirrer, nitrogen purge, water condenser and thermometer.  352. g of molten condensate obtained by condensation of 2.2--5 s (p-hydroxydiphenol) -propane and propylene oxide, and 0.15 g of dibutyltin dilauret are placed in a 1-liter1 dropping funnel, which is pre-purged with nitrogen.  200 ml of methylene chloride are added to the addition funnel to prevent condensation from hardening.  The addition funnel is then placed at the top of the flask and its contents are added dropwise to the flask for 45 minutes, after which the reaction takes place 45 minutes, during which time 300 mg of hydroxyethyl methacrylate are added together with 0.15 g of dibutyl laurate for 3 minutes.  The temperature of the contents of the flask is increased and, when it falls, the flask is heated in a water bath (with methylene chloride reflux), its contents are mixed with nitrogen purging until the infrared spectrum of the obtained product shows only traces of isocyanate groups (about 3 days).  The water bath is then removed and methanol is added to the stirred contents of the flask in order to cause a separation of the polymerizable photo polymer, t.  e.  vinylurethane.  The flasks are allowed to stand, and then the methanol layer is cast and discarded.  Washing with methanol is repeated several times until a pure methanol layer is obtained.  The polymerization prepolymer in the flask is then dried at room temperature under vacuum until a dry foam is obtained.  The foam is then destroyed and dried to remove the trace of methanol.  The preparation of the composition for sealing teeth.  In the absence of blue light for 13, 3 hours, the polymerizing prepolymer powder is dissolved in 10.94 hours / these LEN glycol dimethacrylate, 0.625 hours.  di methylaminoethyl methacrylate is added to the solution, and then 0.0625 h. camphorhinon, 75 h, borosilicate glass powder with a particle size of less than 53 microns and a coating of 1 wt. % 2-methacryloxypropyltrimethoxysil An.  The mixture is stirred and the resulting paste is passed through a roller mill, which is degassed during this passage.  The product is a paste-like tooth-filling material with the following composition,%: Filler75 Polymerized material 25 Polymerized material has the following composition,%: Polymerizable prepolymer 53.5 Dimethyl ethylene glycol acrylate, 43.8 Catalyst2.7 Cylindrical paste samples with 3 diameter mm ir- 2.5 mm long in poetrafluoroethylene forms will be irradiated with light for about 2 minutes.  The hardened specimens are removed from the mold and placed under water at and tested after 1 h, 24 h, and 1 week.  The results are shown in Table.  one.  PRI me R 5.  2,585 h.  the polymerizable prepolymer prepared in Example 4 is dissolved in 2.115 h.  ethylene glycol dimethacrylate.  0.1 h, fluorernal and 0.2 h, dimethylaminoethyl methacrylate are added to a solution of 7.5 ch borosilicate glass powder (as in example 4, but coated with 2 wt. % silane), mixed with resin. with degassing and then, thin samples of the resulting paste harden for about 100 minutes using a low-intensity mercury lamp as a light source, which provides a transmitted radiation of 437 microns.  The solidification depth is 1.5 mesh.  The composition has the following ratio of components, weight. % Filler60 Polymerizable material40 The polymerizable material has the following composition,%; Polymerizable prepolymer DYMET acrylate ethylene glycol Catalyst PRI me R 6.  Paste is prepared and cured, according to Example 5, except that o-naphthol is used instead of fluoroenta.  The cure depth is 2.5 mm, and the composition used is the same as in Example 5.  Examples 7-12.  6.7 hours, the polymerizate of the prepolymer obtained in Example 4 was dissolved in 3.3 hours of methyl methacrylate and 0.2 hours was added to the solution. solution of fluorenone at 4 o'clock  dimethylaminoethyl methacrylate (4 h. ).  15 h.  the filler is mixed with it and the resulting paste is placed in a glass tube with a diameter of 6 mm.  The samples are then solidified by irradiating the fluorescent tube with light for 30.  The cured specimens are cut to lengths of 12 mm and their compressive strength is determined.  The product used has a composition,%: Filler60 Polymerizable material40
    The polymerized material has the following composition,% Polymerizable prepolymer65.5 Methyl methacrylate32.5 Catalyst2.0 The properties of the fillers in examples 7-12 are given in table. 2.,.
    Example 13. 5.5 parts of the polymer of prepolymer prepolymer as in example 4 were dissolved in 4.5 hours, ethylene glycol dimethyl acrylate, and 0.025 parts of N, M-dimethyl-p-toluidine was added to the solution.
    0.3 parts of the mixture is mixed for a few seconds with 0.7 parts of the coating filler using a spatula. Covering the filler is a borosilicate glass powder with a particle size of less than 53 microns and is obtained by coating 23 with glass powder of 0.23 parts methacryloxypropyl trimethoxysilane and 0.03 parts of benzoyl peroxide from methylene chloride.
    The product is a paste-like material for tooth filling, which has the following ratio of components,%: Filler 70 Polymerized material ŠM 30 Polymerizable 1 material has the following composition: Polymerized
    prepolymer54,7
    Dimethacrylate
    ethylene glycol 44,8
    Catalyst0,5
    The resulting paste is placed in cylindrical molds with a size of 3 mm x 3 which lasts for several hours, after which hard samples are removed and tested. Hard material has a compressive strength of 160 N mm and a diametral compressive strength of 30 N.
    Example 14. 33.33 part of the polymerization prepolymer prepared in Example 1 was dissolved in 16.66 parts of methyl methacrylate and 170 h of Ballotnl FP 01 3000 glass beads with an average diameter of 4.4 microns were mixed into the solution. . Then 5 parts of dimethylaminoethyl methacrylate (40%) and benzyl (20%) in methacrylate (40%) are added and the mixture is heated. - An excess of methyl methacrylate is added and the mixture is then stirred for about 15 minutes, after which the excess methacrylate is removed in vacuo.
    The product is a paste-like material for tooth filling, having the following composition,%: Filler75.5
    Polymerizable material 24,5
    The polymerized material has the following composition,%: Polymerizable prepolymer60.5
    Methyl methacrylate 34.0 Catalyst5,5
    The resulting paste is placed in 3 conical cracks, drilled into the dog's canine teeth, and it hardens immediately when using a light-emitting lamp. After 26 months the seal remains in the tooth and there is no noticeable mechanical decrease or weakening in the crack.
    Examples 15-22. The prepolymer prepolymer is prepared according to Example 4. In the absence of blue light, 3.1 prepolymer is dissolved in 2.54 g of monomer and 0.24 dimethylaminoethyl methacrylate and then 0.12 g of benzyl are added to the solution. 14 g of powdered borosilicate glass with a particle size of less than 53 microns, coated with 2 wt.% Fj; -methacryloxypropyl trimethoxysilane is admixed to the mixture (in such quantity that the filler contains 70% by weight of the composition). and the resulting paste is passed through a roller mill, as a result of which it is degassed.
    The product is a paste-like material for tooth filling, having the following composition,%: Filler70
    Polymerizable material30 Polymerizable material has the following composition,%: Polymerizable prepolymer 51.6 Saturated
    monomer42,4
    Catalyst6.0
    Cylindrical paste samples with a diameter of 3 mm and a length of 2.5 mm are solidified in polytetrafluoroethylene forms by irradiating for about 1 hour with a Thorn illuminating lamp. Samples are removed after 1 h and tested for compressive strength and hardness.
    The properties of the compositions according to examples 1522 are given in table. 3
    Example23. A. The procedure of Example 21 is carried out, except that after irradiating the sample for 1 hour, it is removed from the mold and allowed to stand for 2 days before testing.
    B. For comparison, Procedure A is carried out using different polymerizing prepolymers.
    The prepolymers were prepared as follows.
    Freshly distilled 2,4-toluene diisocyanate is poured into a flask with methylene chloride and a mixture of 2,2-propane-bis- (3- (4-phenoxy) -1,2-hydroxy propane-1) -methacrylate and dibutyl tin dilaurate is added . The reaction is continued until the infrared analysis of the mixture shows that only traces of isocylate groups are present. Methanol is added to the flask to cause separation of the obtained prepolymer, which is then dried and finally ground. C. Also for comparison, Procedure A was carried out using a prepolymerizing prepolymer as, except that phenolisocyanate is used instead of 2,4-toluene diisanes cyanate. e. Perform procedure A using a prepolymer as in, but using anidene diisoci. Nata instead of 2,4-toluene diisocyanate. E. For comparison, Procedure A was carried out using polymerization degos prepolymer prepared as in B, but using 4,4-diisocyaniphenylmethane instead of 2,4-toluene diisocyanate. 4 shows the characteristics of the compositions obtained according to Example A-E Pr and Me p 24. Preparation for vinyl. tana. A 35.2 g {0.1 mol) of the oxypropylated bisfepol A is dissolved in 100 g of methylene chloride and the resulting solution is added as follows: gl to a solution of 33.6 g (0.2 mol) of hexamethylene diisocyanate 100 g of chloride methylene in atmbsfe nitrogen gas. 4 drops of dibouti, tin dilaurate are added as a catalyst. The mixture is stirred under nitrogen for 1 hour, then it is heated under reflux for 9 hours. The mixture is then cooled and a solution of 26 g (0.2 mol) of 2-hydroxyethyl methacrylate and 100 g of chlorine methylene is added, after which the mixture is heated under reflux for 3 hours. The mixture is then cooled and the resulting polymerizable pre-polymer is isolated as a viscous resin by treating the mixture with petroleum ether, followed by removal of the remaining solvent on a rotary evaporator. The filler was used for the following content,%: Borosilicate glass in the form of a powder,% (diameter less than 53 microns) 75 Polymerizable material,% 25 The filler was treated with 1% by weight with a silane (A174) combination agent. Preparation of tooth-filling compound,%: Visc resin - (polymerized prepolymer) 53.5 ethylene glycol dimethacrylate 43.8 Catalyst2.7 Catalyst contains (by weight): Camphorquinone 0.06525L Dimethylaminoethylmethacrylate, 625 Example25. 52.4 g (0.2 mol) of 4,4-dicyclohexylmethane-diisocyanate are placed in a flask together with 30 ml of methylene chloride in a nitrogen atmosphere, 35.2 g (0.1 mol) of the oxypropylated bisphenol A, dissolved in 50 ml of dry chloride methylene and the solution is washed with 20 ml doses of dry methylene chloride in an addition funnel. 10 drops of dibutyl tin dilaurate are added to the solution from the dropping funnel. The mixture in the flask is heated until a gentle reflux of methylene chloride begins, and then the solution is added from the dropping funnel over 1 hour with stirring. Stirring is continued for 1.5 hours, after which 26 g (0.2 mol) of hydroxyethyl methyl acrylate and 10 drops of dibutyl tin dilute are added over a 15 minute period from the dropping funnel. The mixture was stirred for 3 hours and then left to stand for 70 hours, Analysis of the mixture using IR spectroscopy indicated the presence of residual isocyanate, and the mixture was left to stand for another 48 hours. The resulting polymerizable prepolymer was isolated. in the form of a solid as a result of treating the mixture with petroleum ether, followed by removal of the residual solvent on a rotary evaporator. The tooth-filling composition is prepared from a solid polymer according to the described method, and a recipe is obtained from it, according to Example 24. The samples are cured according to the procedure also described in Example 24. The prepolymer paste has good flow properties and the cured material is very transparent. The cure depth reached in 1 minute is 6.1 mm, and after being immersed in water for 24 hours at 37 s (Example 24), the cured material has a compressive strength (average) of 264.2 N mm and a tensile strength (average) 41.7 N. Example 26: A composition for filling teeth is prepared, prepared. from it, the recipe and cure as described in example 25, except that 34.8 g (0.2 mol) of 2,4-toluene-diisocyanate is used instead of dicyclohexyl methane diisocyanate. The paste preparation has good flow properties and the cured material is transparent. The cure depth is b, 5 mm. After immersion in water for 24 hours, the substance has compressive strength
    (average), equal to 290.65 N mm, and ultimate tensile strength average) 47.6 N mm.
    The proposed composition allows to increase the strength of its fit to the walls of the tooth.
    Table
    79962924
    23
    Continued table. 3
    Ethylene glycol 184
    Dimethacrylate
    allyl methacrylate155
    37 32
    28
    34
    Note. -If, the material showed very poor cure, and no stretch samples were obtained. The invention Composition for tooth filling, containing an inorganic filler and a binding agent with the following ratio: inorganic filler 60-90 wt.%, and binding agent 10-40 wt.%, o t h and h and sch so that, in order to increase the strength of its adherence to the tooth staples, the binding agent is a mixture of vinylurethane, obtained by the reaction of a diol with diisocia
    85
    52
    Table4
    105 88
    Sample is crushed
    96 naty and hydroxylamine acrylate or methacrylate, vinyl monomer and catalyst in the following ratio of components, wt.%; Vinyl monomer32.5-50.0 Catalyst 0.5-6.0 Vinylurethane Else Sources of information taken into account during the examination 1. IT patent 3452437, cl. A 61 K 5/0, 1962.
    权利要求:
    Claims (1)
    [1]
    Claim
    Composition for dental fillings, 40 containing an inorganic filler and a bonding agent in the following ratio: inorganic filler 60-90 wt.%, And a bonding agent 10-40 wt.%, Characterized in that, in order to increase the adhesion strength it to the walls of the tooth, the binding agent is a mixture of vinylurethane obtained by the reaction of a diol with diisocyanate and hydroxyalkyl acrylate or methacrylate, a vinyl monomer and a catalyst in the following ratio of components, Vinyl monomer Catalyst Vinyl urethane wt.%:
    32.5-50.0 0.5-6.0 Else
    类似技术:
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    同族专利:
    公开号 | 公开日
    DK137522B|1978-03-20|
    NL7405457A|1974-10-28|
    CH597858A5|1978-04-14|
    JPS5042696A|1975-04-17|
    JPS5533687B2|1980-09-02|
    FI58065B|1980-08-29|
    YU39720B|1985-04-30|
    ES425620A1|1977-02-01|
    DE2419887A1|1974-11-21|
    AR205444A1|1976-05-07|
    NO143127C|1980-12-29|
    IE39486L|1974-10-24|
    AT338436B|1977-08-25|
    IL44696D0|1974-07-31|
    SE421994B|1982-02-15|
    ATA339774A|1976-12-15|
    YU114974A|1982-02-28|
    NO143127B|1980-09-15|
    FI58065C|1980-12-10|
    IE39486B1|1978-10-25|
    IL44696A|1977-02-28|
    FR2226984B1|1978-01-20|
    MC1015A1|1975-02-28|
    IT1046789B|1980-07-31|
    BR7403337D0|1975-01-28|
    NO741411L|1974-10-25|
    DE2419887C2|1982-07-01|
    AU6814474A|1975-10-23|
    DK137522C|1978-09-04|
    FR2226984A1|1974-11-22|
    LU69906A1|1974-08-06|
    MX3035E|1980-03-03|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3254411A|1962-11-05|1966-06-07|Johnson & Johnson|Tooth cavity filling and method of filling teeth|
    US3629187A|1969-06-25|1971-12-21|Dentsply Int Inc|Dental compositions containing adduct of 2 2' - propane bis 3--1 2-hydroxy propane - 1 - methacrylate and isocyanate|
    US3709866A|1970-06-01|1973-01-09|Dentsply Int Inc|Photopolymerizable dental products|
    GB1401805A|1972-03-15|1975-07-30|Amalgamated Dental Co Ltd|Dental filling materials|
    GB1428672A|1972-04-25|1976-03-17|Amalgamated Dental Co Ltd|Polymerizable compositions suitable for dental use|
    GB1430303A|1973-03-15|1976-03-31|Amalgamated Dental Co Ltd|Dental filling materials|CA1117685A|1976-11-15|1982-02-02|Narayanan Madhavan|One paste polymeric dental restorativecomposition|
    DE2964564D1|1978-12-18|1983-02-24|Ici Plc|Dental compositions comprising a selected vinyl urethane prepolymer and processes for their manufacture|
    ZA796404B|1978-12-18|1981-03-25|Ici Ltd|Dental compositions|
    DE3001616A1|1980-01-17|1981-07-23|ESPE Fabrik pharmazeutischer Präparate GmbH, 8031 Seefeld|METHOD FOR PRODUCING DENTAL SPARE PARTS BY PHOTOPOLYMERIZING A DEFORMABLE DIMENSION|
    JPS6325562B2|1980-02-27|1988-05-26|Kuraray Co|
    AT11909T|1980-07-23|1985-03-15|Blendax Werke Schneider Co|ADDUCTS FROM DIISOCYANATES AND METHACRYLOYL ALKYL ETHERS, ALKOXYBENZOLS OR ALKOXYCYCLOALCANES AND THEIR USE.|
    USRE35264E|1981-05-04|1996-06-04|Dentsply Research & Development Corp.|Dental adhesive system|
    SE430697B|1982-05-04|1983-12-05|Protector Agentur Ab|INACTIVATED POLYURETHANE, SET TO PREPARE THIS AND USE IT|
    DE3506020A1|1985-02-21|1986-08-21|Etablissement Dentaire Ivoclar, Schaan|METHOD FOR THE PRODUCTION OF ARTIFICIAL TEETH OR TEETH PARTS AND FOR THIS SUITABLE BEARABLE DENTAL MATERIAL|
    CA1302659C|1986-10-24|1992-06-09|Hans-Peter K. Gribi|Dental impression material|
    US4892478A|1988-03-21|1990-01-09|Dentsply Research & Development Corp.|Method of preparing dental appliances|
    JP2556763B2|1990-09-26|1996-11-20|昭和高分子株式会社|Urethaneacrylate polymerizable composition|
    EP1632211A1|2004-09-07|2006-03-08|S & C Polymer Silicon- und Composite-Spezialitäten GmbH|Dental resin-modified polyalkenoate cement composition|
    DE102009016025B4|2009-04-02|2014-12-11|Voco Gmbh|Plastic modified glass ionomer cement, its use and process for its preparation|
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    US9023916B2|2010-09-30|2015-05-05|Voco Gmbh|Composite material comprising a monomer with a polyalicyclic structure element|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB1927773|1973-04-24|
    GB1927073A|GB1465897A|1973-04-24|1973-04-24|Dental compositions|
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