CA1238996A - Inorganic-organic fillers, a process for their preparation and their use in polymerisable compositions - Google Patents
Inorganic-organic fillers, a process for their preparation and their use in polymerisable compositionsInfo
- Publication number
- CA1238996A CA1238996A CA000468012A CA468012A CA1238996A CA 1238996 A CA1238996 A CA 1238996A CA 000468012 A CA000468012 A CA 000468012A CA 468012 A CA468012 A CA 468012A CA 1238996 A CA1238996 A CA 1238996A
- Authority
- CA
- Canada
- Prior art keywords
- filler
- weight
- inorganic
- meth
- inorganic core
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
Abstract
Inorganic-organic fillers, a process for their preparation and their use in polymerisable compositions ABSTRACT OF THE DISCLOSURE
A filler for a polymerizable composition comprising an inorganic core of particles with a particle size of 10 to 500 nm, a first shell of vinylsilane and a second shell of a (meth)acrylate polymer. The filler is then used to prepare dental moldings of acrylates in conventional manner.
The moldings are very hard and abrasion resistant.
A filler for a polymerizable composition comprising an inorganic core of particles with a particle size of 10 to 500 nm, a first shell of vinylsilane and a second shell of a (meth)acrylate polymer. The filler is then used to prepare dental moldings of acrylates in conventional manner.
The moldings are very hard and abrasion resistant.
Description
~2~
.,,,~
-, The invention relates to a filler for poLymeris-able compositions, in particular dental mater;als, cons;st-ing of an inorganic core, a 1st shell of a polymerised vinylsilane and a 2nd shell of acrylat~or methacrylate 5 polymers.
Polymer systems filled with ;norganic fillers are w;dely used ;n dental materials. Thus, hardenable mixtures of ~meth)acrylic acid esters, as polymerisable binders, and fine-particled inorganic f;llers are in general used 10 as dental filling materials based on plastics.
These fillers can be classified according to their particle size as "macrof;llers", with a particle size of about 1 em to about 50 sum (preferably about 30 sum) and as "microfillers" with a particle size of about 5 - 500 nm.
15 Dental materials based on "macrofillers" are described, ; for example, in U.S. Patent Specification 3,066,112, U.S.
Patent Specification 3,926,906, DE-OS (German Published Specification) 2,357,324 and DE-OS (German Published Specificat;on) 2,419,~87.
DE-OS (German Published Specification) 2,403,211 and DE-OS (German Published Specification) 2,462,271 dis-close materials for dental purposes which contain, as an inorganic filler, exclusively microfine silicon dioxide with a particle size of 5 to 70û nm. Compared with the 25 "macrofiller products", the "m;crofiller products" are significantly easier to polish, but in general have a lower degree of filling, which has an adverse effect on some physical properties, such as polymerisation shrinkage, coefficient of thermal expansion and absorption of waxer.
30 Moreover, formulations of "microfillers" and palymerisable b;nders have poor processing properties because of their high tackiness. Various routes have been taken to counter-act the difficulties of incorporating "microfillers" into monomeric binders. Thus, it is possible to replace all or Le A 22 701 some of the "microfiller particles" by "microfiller"-containing prepolymers in chip form. The incorporation of "microfiller particles" into bead polymers is a further improvement (European Patent A-001,190). The use of filler-containing prepolymers in chip or bead form leads to "microfiller products" with a filler content of about 50% by weight as the upper limit. Higher degrees of filling can be achieved by agglomerating the "microfillers"
before use and grinding the agglomerates to granules, but losses must be tolerated in respect of homogeneity and ease of polishing of the dental material (PCT~EP 80/00135).
Coating of "macrofillers" with organic polymers for the purpose of increasing the ease of incorporation into dental materials is a known method. Thus, DE-OS (German Published Specification) 1,937,871 describes a finely dlvided silicon dioxide or silicate filler coated with a vinylsilane as a base coat and with an acrylic polymer. European Patent A-0,047,971 likewise discloses mineral particles coated with plastic. Glass granules coated with synthetic polymers are known as fillers for dental filling compositions from Japanese Patent A 74-042,905.
However, these known coating processes cannot be applied in the manner described to "microfillers", since "microfillers" tend to form agglomerates during after-treatment because of their extremely low particle si2e and high specific surface area, which means that the advantageous properties of the "microfillers" are lost.
I
The object of the present invention is to provide a filler based on "microfillers", fox dental materials, which allows a high degree of filling and leads to materials which can easily be polished and have high mechanical strengths.
ccording to one aspect of -the present invention there is provided a filler for a polymerisable composition comprising an inorganic core, a first shell of vinylsilane and a second shell of (meth)acrylate polymers, characterised in that the in-organic core comprises particles with a particle size of 10 to 500 nm.
The filler according to the invention can be obtained by dispersing a highly disperse filler in an organic solvent, silanising the filler in a first step with a mixture of vinyl-silane, water and acid and encasing the product with (meth)acrylate polymers in a second step by polymerisation.
Suitable highly disperse fillers are all the conventional inorganic fillers with particle si2es of 10 - 500 nm, in particular 10 - 100 nm, preferably those based on aluminium oxide, silicon dioxide and silicates. Silicon dioxide and aluminium dioxide obtained by flame hydrolysis and having a particle size of 10 to 40 nm and a BET surface area of 30 to 300 m /g, preferably 40 to 200 m2/g, are particularly preferred.
The vinylsilanes which are known per se from the above-mentioned printed publications, such as, for example, vinyltri-ethoxysilane, vinyltrimethoxysilane, Y -methacryloxypropyltri-~2~
- 3a -methoxysilane, Y-methacryloxypropyl-tri(2-methoxy)-silane or vinyltriacetoxysilane can be used, for example, for the first shell of vinylsilane. ~-Methacryloxypropyltrimethoxysilane is preferably used. The amount of silane compound is preferably
.,,,~
-, The invention relates to a filler for poLymeris-able compositions, in particular dental mater;als, cons;st-ing of an inorganic core, a 1st shell of a polymerised vinylsilane and a 2nd shell of acrylat~or methacrylate 5 polymers.
Polymer systems filled with ;norganic fillers are w;dely used ;n dental materials. Thus, hardenable mixtures of ~meth)acrylic acid esters, as polymerisable binders, and fine-particled inorganic f;llers are in general used 10 as dental filling materials based on plastics.
These fillers can be classified according to their particle size as "macrof;llers", with a particle size of about 1 em to about 50 sum (preferably about 30 sum) and as "microfillers" with a particle size of about 5 - 500 nm.
15 Dental materials based on "macrofillers" are described, ; for example, in U.S. Patent Specification 3,066,112, U.S.
Patent Specification 3,926,906, DE-OS (German Published Specification) 2,357,324 and DE-OS (German Published Specificat;on) 2,419,~87.
DE-OS (German Published Specification) 2,403,211 and DE-OS (German Published Specification) 2,462,271 dis-close materials for dental purposes which contain, as an inorganic filler, exclusively microfine silicon dioxide with a particle size of 5 to 70û nm. Compared with the 25 "macrofiller products", the "m;crofiller products" are significantly easier to polish, but in general have a lower degree of filling, which has an adverse effect on some physical properties, such as polymerisation shrinkage, coefficient of thermal expansion and absorption of waxer.
30 Moreover, formulations of "microfillers" and palymerisable b;nders have poor processing properties because of their high tackiness. Various routes have been taken to counter-act the difficulties of incorporating "microfillers" into monomeric binders. Thus, it is possible to replace all or Le A 22 701 some of the "microfiller particles" by "microfiller"-containing prepolymers in chip form. The incorporation of "microfiller particles" into bead polymers is a further improvement (European Patent A-001,190). The use of filler-containing prepolymers in chip or bead form leads to "microfiller products" with a filler content of about 50% by weight as the upper limit. Higher degrees of filling can be achieved by agglomerating the "microfillers"
before use and grinding the agglomerates to granules, but losses must be tolerated in respect of homogeneity and ease of polishing of the dental material (PCT~EP 80/00135).
Coating of "macrofillers" with organic polymers for the purpose of increasing the ease of incorporation into dental materials is a known method. Thus, DE-OS (German Published Specification) 1,937,871 describes a finely dlvided silicon dioxide or silicate filler coated with a vinylsilane as a base coat and with an acrylic polymer. European Patent A-0,047,971 likewise discloses mineral particles coated with plastic. Glass granules coated with synthetic polymers are known as fillers for dental filling compositions from Japanese Patent A 74-042,905.
However, these known coating processes cannot be applied in the manner described to "microfillers", since "microfillers" tend to form agglomerates during after-treatment because of their extremely low particle si2e and high specific surface area, which means that the advantageous properties of the "microfillers" are lost.
I
The object of the present invention is to provide a filler based on "microfillers", fox dental materials, which allows a high degree of filling and leads to materials which can easily be polished and have high mechanical strengths.
ccording to one aspect of -the present invention there is provided a filler for a polymerisable composition comprising an inorganic core, a first shell of vinylsilane and a second shell of (meth)acrylate polymers, characterised in that the in-organic core comprises particles with a particle size of 10 to 500 nm.
The filler according to the invention can be obtained by dispersing a highly disperse filler in an organic solvent, silanising the filler in a first step with a mixture of vinyl-silane, water and acid and encasing the product with (meth)acrylate polymers in a second step by polymerisation.
Suitable highly disperse fillers are all the conventional inorganic fillers with particle si2es of 10 - 500 nm, in particular 10 - 100 nm, preferably those based on aluminium oxide, silicon dioxide and silicates. Silicon dioxide and aluminium dioxide obtained by flame hydrolysis and having a particle size of 10 to 40 nm and a BET surface area of 30 to 300 m /g, preferably 40 to 200 m2/g, are particularly preferred.
The vinylsilanes which are known per se from the above-mentioned printed publications, such as, for example, vinyltri-ethoxysilane, vinyltrimethoxysilane, Y -methacryloxypropyltri-~2~
- 3a -methoxysilane, Y-methacryloxypropyl-tri(2-methoxy)-silane or vinyltriacetoxysilane can be used, for example, for the first shell of vinylsilane. ~-Methacryloxypropyltrimethoxysilane is preferably used. The amount of silane compound is preferably
2 - 40% by weight, particularly preferably 5 - 25% by weight, based on the highly disperse filler.
To prepare the fillers according to the invention, it is necessary to maintain defined silanisation conditions. The silane compound is converted into an activated form in a first reaction stage by reaction with water. In this preliminary reaction, the less reactive alkoxy or acetoxy groups of the silane compound are probably hydrolysed to the more reactive silanol groups. This reactive mixture is not stable on storage and must be freshly prepared each time before the silanisation reaction. The
To prepare the fillers according to the invention, it is necessary to maintain defined silanisation conditions. The silane compound is converted into an activated form in a first reaction stage by reaction with water. In this preliminary reaction, the less reactive alkoxy or acetoxy groups of the silane compound are probably hydrolysed to the more reactive silanol groups. This reactive mixture is not stable on storage and must be freshly prepared each time before the silanisation reaction. The
3~
\
6, react;on t;rne requ;red for the s;lane-water prel;m;nary react;on depends on the react;on temperature and ;s as a rule ;n the range from 15 m;nutes to 2 hours at room tem-perature. Part;cularly good results are ach;eved if the S water and silane compound are used ;n approximately the same amounts by we;ght. The most advantageous react;v;ty of the s;lane compound occurs at the t;me at wh;ch the ;nitially two-phase water/silane mixture has just become a s;ngle-phase system. E;ther m;neral ac;ds or organic ac;ds can be used 35 the catalyst. Acryl;c ac;d ard meth-acryl;c cad for example, are part;cularly su;table. The ac;d ;s preferably used ;n amounts of 0.1 to 5 X by weight, part;cularly preferably 0.5 to 2 by weight, based on the s;lane compound.
The s;lan;sat;on ;s preferably carr;ed out ;n the presence of an inert organ;c solvent, such as, for example, acetone, ethyl acetate, chloroform or methylene chlor;de.
The h;ghly d;sperse f;ller ;s preferably d;spersed ;n the organ;c solvent ;n a concentrat;on of 5 - ~0 % by we;ght, part;cularly preferably 15 - 25 % by weight, w;th the a;d of a h;gh-speed st;rrer, and the prepared act;ve s;lane/
water m;xture ;s added. The silan;sat;on reaction can be carr;ed out between 0 and 100C, for example at room temperature, but advantageously at elevated temperature, for example at the bo;l;ng po;nt of the solvent.
The react;on t;me ;s ;n general a Few hours.
During the s;lan;sat;on, the viscos;ty of the dispers;on decreases, so that the end of the react;on can be deter-m;ned ;n a s;mple manner by cont;nuous measurement of the v;scos;ty.
To bu;ld up the 2nd shell, (meth~acrylate monomers and a polymer;sat;on ;n;t;ator are added to the dispersion of the silanised f;ller in an inert organ;c solvent and the polymerisation reaction is started. The monomers can be added all at once in one portion at the start of the react;on. However, it ;s more advantageous to meter the Le A 22 701 . _ ~38~
monomers and the polymerisation initiator into the react;on m;xture in portions over a longer per;od of t;me.
Su;table (meth)acrylate monomers are both mono-functional (meth)acrylates and di- and tr;-(meth~acryLates.
In a particular embodiment of the present ;nvent;on, at least a proportion of di- or tri-(meth)acrylates is added, so that the Znd shell is crosslinked.
Examples of mono-(meth)acrylates which can be used are: methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth~acrylate, cyclohexyl (meth)acrylate and dihydrod;cyclopentad;enyl (meth)acryl-ate.
Examples of di(meth)acrylates wh;ch may be men-t;oned are: ethylene glycol di(meth)acrylate, d;ethylene glycol d;(meth)acrylate, triethylene glycol di(meth)acryl-ate, neopentylglycol di(meth)acrylate, 1,12-dodecane d;-(meth)acrylate, and furthermore der;vat;ves of b;sphenol A, such as ~,2-b;s-4(2-hydroxy-3~methacryloyloxypropyl)-phenyl-propane (bis GMA) and urethane di(meth)acrylates, such as are described, for example, in U.S. Patent Speci-fications 3,425,988, 3,709,866 and 3,629,187.
Examples of possible tri(meth)acrylates are:
glycerol tri(meth)acrylate, trimethylolpropane tri(meth)-acrylate and pentaerythritol tri~meth)acrylate.
The term (meth)acrylate means both methacrylate and acrylate. The methacrylates are preferably used for the preparation of the fillers according to the invention.
Besides the (meth)acrylates, it is also possible to use up to 20 Z by weight, based on the sum of the ~meth)acryl-ate monomers, of other vinyl or vinylidene monomers, such as, for example, styrene, ~-methylstyrene, acrylonitrile or vinylacetate. The (meth)acrylate monomers are prefer-ably used ;n amounts ox 3-100 Z by weight, particularly preferably 10-50 % by we;ght, based on the highly disperse Miller. The choice of the (meth)acrylate monomers used is made in v;ew of the desired ;ntended use of the filler Le A 22 701 ~23~6 accord;ng to the invention. It ;s thus advantageous, for example, for use in teeth made of polymethylmethacrylate plastic, to copolymerise at least a proport;on of methyl methacryLate in the 2nd shell in order to achieve a good 5 tolerance.
The customary soluble agents which form free radi-cals can be used to initiate the polymerisation; examples which may be mentioned are: peroxide and azo compounds, such as dibenzoyl peroxide, dilauroyl peroxide, cyclohexyl 10 percarbonate and azoisobutyrod;nitrile. Mixtures of poly-merisation initiators with different decomposition tempera-tures are also particularly suitable. The polymerisation is started by heat;ng to the decompos;t;on temperature of the polymerisation ;n;tiator~ The polymerisation can be 15 carried out under increased pressure, for example under a nitrogen pressure of 2 to 6 bar. The mixture is prefer-ably s.irred with a high-speed stirrer during the polymer-;sat;on.
The filler according to the invention can be 20 obtained from the polymerised dispersion by evaporating off the solvent. It is also possible to flocculate out the polymer, for example by addition of methanol, and to filter it off. It is particularly advantageous to use a spray-dry;ng process ;n wh;ch a f;ne-part;cled, free-25 flow;ng product ;s obta;ned~
The filler according to the invent;on, ;n part;-cular the f;ller isolated by spray-dry;ng, can advantage-ously be used ;n polymerisable composit;ons, in particular ;n the preparation of dental plastics. The filler is 30 easily wettable, outstand;ngly dispersible and can be in-corporated w;th h;gh degrees of filling ;nto monomeric binders Shaped articles, for example false teeth or dental fillings, containing the filler according to the invention, are d;stinguished by a high mechan;cal strength 35 and, in particular, a high abrasion resistance.
The polymerisable compositions according to the Le A 22 701 ;nvention conta;n 20 to 65 % by weight, preferably 20 ts by weight and in particular 25 to 45 % by we;ght, of a polymer;sable monomer, 10 to 75 % by weight, prefer-ably 20 to 75 % by weight and in particular 30 to 70 % by 5 weight of the f;ller accord;ng to the ;nvent;on and, ;f appropr;ate, further inorganic or organic f;llers, poly-merisation initiators, inhibitors, dyestuffs and other additives, which are known per se. If large amounts of polyfunctional monomers (crossl;nking agents) are used and 10 for certa;n intended uses ;t may be advantageous to add plasticisers to the polymerisable compositions according to the invention in order to reduce the brittleness.
H;gh molecular weight plast;c;sers which are known per se, in particular those based on polyurethanes, polycarbonates, 15 polyesters and polyethers, are above all particularly suitable. Polyesters and polyester-carbonates, which are described ;n German Patent Application P 33 16 851.2 are preferred. Examples of possible polymerisable monomers and polymerisation initiators are the compounds mentioned 20 above in connection with the preparation of the 2nd shell of the filler. The polymerisable compositions are parti-cularly suitable for the preparation of shaped dental articles, and also as bone cements and for other ortho-paedic surfaces.
25 Example 1 19.8 kg of methylene chloride and 3.8 kg of highly d;sperse s;l;con d;ox;de (part;cle size about 20 nm~ BET
surface area 50 m2/g) are weighed into a 40 litre stirred autoclave which can be heated, and the stirrer 30 speed is adjusted to 400 rpm. 760 g of y methacryloxy-propyltr;methoxysilane, 980 g of deionised water and 10.4 9 of methacrylic acid are mixed in a separate gl355 vessel.
As soon as the mixture ;s a single phase system (after about 4n minutes at room temperature ;t ;s added in one 35 portion to the st;rred autoclave. The temperature in the stirred autoclave is kept at 40C for 20 hours, and Le A 22 7û1 .
123~399~;
0.38 kg of methyl methacrylatet 0.38 kg of isobutyl methacrylate, 8 g of ethyLene d;methacrylate 3nd 2~ 9 of azoisobutyrodinitrile are then added, a pressure of 5 bar of N2 is applied and the temperature is kept a 70C for 5 3 hours and then at 80C for a further 3 hours. After cooling, the dispersion is diluted with 10 kg of methylene chloride and subjected to a spray-drying process. 5.1 kg of fine-particled filler are obtained.
Example 2 1û Example 1 is repeated, the following amounts being used: 19.8 kg of methylene chlor;de, 3r8 kg of highly d;s-perse silicon dioxide (particle size about 20 nm, BET
surface area 50 m2/g), 456 9 of methacryloxypropyltri-methoxysilane, 588 9 of deionised water, 6 g of methacrylic 15 acid, 550 9 of methyl methacrylate, 11 g of ethylene di-methacrylate and 20 9 of azoisobutyrodinitrile. 4.8 kg of fine-particled filler are obtained.
Example 3 65 g of bisphenol A diglycidyl dimethacrylate, 20 35 9 of triethylene glycol dimethacrylate~ 318 9 of the fine-particled filler of Example 1, 2 g of dibenzoyl per-oxide and small amounts (< 0.1 9) of customary pigments are kneaded to a paste in a kneader. To produce teeth, this paste is pressecl into mouLds and hardened at 130C in 25 the course of 6 m;nutes. The result;ng teeth are distin-guished by be;ng very hard and having a high abrasion resistance.
Example 4 75 g of methyl methacrylate, 20 9 of ethylene 30 dimethacrylate, 5 9 of a polyester containing polycarbon-ate groups (Example 3 of DE-OS tGerman Published Specific-ation) 2,732,718), 20 9 of diben~oyl peroxide, 30 9 of polymethyl-methacrylate bead polymer (d50: 45 ~Im~ Clz ]
in CHCl3: 1.8 dl/g) and 220 9 of fine-particled filler 35 from ExampLe Z are kneaded to a paste~like composition in a kneader. This compos;tion ;s act;vated w;th 2 g of Le 22 701 ~a~3~
_ 9 _ d;benzoyl peroxide and coloured the colour of teeth w;th the customary pigments. After a maturing time of 30 min-utes, the composit;on ;s pressed into teeth moulds and hardened at 120C for 8 minutes. The resulting teeth S are dist;ngu;shed by be;ng very hard and hav;ng a high abras;on res;stance.
Le A 22 7Q1
\
6, react;on t;rne requ;red for the s;lane-water prel;m;nary react;on depends on the react;on temperature and ;s as a rule ;n the range from 15 m;nutes to 2 hours at room tem-perature. Part;cularly good results are ach;eved if the S water and silane compound are used ;n approximately the same amounts by we;ght. The most advantageous react;v;ty of the s;lane compound occurs at the t;me at wh;ch the ;nitially two-phase water/silane mixture has just become a s;ngle-phase system. E;ther m;neral ac;ds or organic ac;ds can be used 35 the catalyst. Acryl;c ac;d ard meth-acryl;c cad for example, are part;cularly su;table. The ac;d ;s preferably used ;n amounts of 0.1 to 5 X by weight, part;cularly preferably 0.5 to 2 by weight, based on the s;lane compound.
The s;lan;sat;on ;s preferably carr;ed out ;n the presence of an inert organ;c solvent, such as, for example, acetone, ethyl acetate, chloroform or methylene chlor;de.
The h;ghly d;sperse f;ller ;s preferably d;spersed ;n the organ;c solvent ;n a concentrat;on of 5 - ~0 % by we;ght, part;cularly preferably 15 - 25 % by weight, w;th the a;d of a h;gh-speed st;rrer, and the prepared act;ve s;lane/
water m;xture ;s added. The silan;sat;on reaction can be carr;ed out between 0 and 100C, for example at room temperature, but advantageously at elevated temperature, for example at the bo;l;ng po;nt of the solvent.
The react;on t;me ;s ;n general a Few hours.
During the s;lan;sat;on, the viscos;ty of the dispers;on decreases, so that the end of the react;on can be deter-m;ned ;n a s;mple manner by cont;nuous measurement of the v;scos;ty.
To bu;ld up the 2nd shell, (meth~acrylate monomers and a polymer;sat;on ;n;t;ator are added to the dispersion of the silanised f;ller in an inert organ;c solvent and the polymerisation reaction is started. The monomers can be added all at once in one portion at the start of the react;on. However, it ;s more advantageous to meter the Le A 22 701 . _ ~38~
monomers and the polymerisation initiator into the react;on m;xture in portions over a longer per;od of t;me.
Su;table (meth)acrylate monomers are both mono-functional (meth)acrylates and di- and tr;-(meth~acryLates.
In a particular embodiment of the present ;nvent;on, at least a proportion of di- or tri-(meth)acrylates is added, so that the Znd shell is crosslinked.
Examples of mono-(meth)acrylates which can be used are: methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth~acrylate, cyclohexyl (meth)acrylate and dihydrod;cyclopentad;enyl (meth)acryl-ate.
Examples of di(meth)acrylates wh;ch may be men-t;oned are: ethylene glycol di(meth)acrylate, d;ethylene glycol d;(meth)acrylate, triethylene glycol di(meth)acryl-ate, neopentylglycol di(meth)acrylate, 1,12-dodecane d;-(meth)acrylate, and furthermore der;vat;ves of b;sphenol A, such as ~,2-b;s-4(2-hydroxy-3~methacryloyloxypropyl)-phenyl-propane (bis GMA) and urethane di(meth)acrylates, such as are described, for example, in U.S. Patent Speci-fications 3,425,988, 3,709,866 and 3,629,187.
Examples of possible tri(meth)acrylates are:
glycerol tri(meth)acrylate, trimethylolpropane tri(meth)-acrylate and pentaerythritol tri~meth)acrylate.
The term (meth)acrylate means both methacrylate and acrylate. The methacrylates are preferably used for the preparation of the fillers according to the invention.
Besides the (meth)acrylates, it is also possible to use up to 20 Z by weight, based on the sum of the ~meth)acryl-ate monomers, of other vinyl or vinylidene monomers, such as, for example, styrene, ~-methylstyrene, acrylonitrile or vinylacetate. The (meth)acrylate monomers are prefer-ably used ;n amounts ox 3-100 Z by weight, particularly preferably 10-50 % by we;ght, based on the highly disperse Miller. The choice of the (meth)acrylate monomers used is made in v;ew of the desired ;ntended use of the filler Le A 22 701 ~23~6 accord;ng to the invention. It ;s thus advantageous, for example, for use in teeth made of polymethylmethacrylate plastic, to copolymerise at least a proport;on of methyl methacryLate in the 2nd shell in order to achieve a good 5 tolerance.
The customary soluble agents which form free radi-cals can be used to initiate the polymerisation; examples which may be mentioned are: peroxide and azo compounds, such as dibenzoyl peroxide, dilauroyl peroxide, cyclohexyl 10 percarbonate and azoisobutyrod;nitrile. Mixtures of poly-merisation initiators with different decomposition tempera-tures are also particularly suitable. The polymerisation is started by heat;ng to the decompos;t;on temperature of the polymerisation ;n;tiator~ The polymerisation can be 15 carried out under increased pressure, for example under a nitrogen pressure of 2 to 6 bar. The mixture is prefer-ably s.irred with a high-speed stirrer during the polymer-;sat;on.
The filler according to the invention can be 20 obtained from the polymerised dispersion by evaporating off the solvent. It is also possible to flocculate out the polymer, for example by addition of methanol, and to filter it off. It is particularly advantageous to use a spray-dry;ng process ;n wh;ch a f;ne-part;cled, free-25 flow;ng product ;s obta;ned~
The filler according to the invent;on, ;n part;-cular the f;ller isolated by spray-dry;ng, can advantage-ously be used ;n polymerisable composit;ons, in particular ;n the preparation of dental plastics. The filler is 30 easily wettable, outstand;ngly dispersible and can be in-corporated w;th h;gh degrees of filling ;nto monomeric binders Shaped articles, for example false teeth or dental fillings, containing the filler according to the invention, are d;stinguished by a high mechan;cal strength 35 and, in particular, a high abrasion resistance.
The polymerisable compositions according to the Le A 22 701 ;nvention conta;n 20 to 65 % by weight, preferably 20 ts by weight and in particular 25 to 45 % by we;ght, of a polymer;sable monomer, 10 to 75 % by weight, prefer-ably 20 to 75 % by weight and in particular 30 to 70 % by 5 weight of the f;ller accord;ng to the ;nvent;on and, ;f appropr;ate, further inorganic or organic f;llers, poly-merisation initiators, inhibitors, dyestuffs and other additives, which are known per se. If large amounts of polyfunctional monomers (crossl;nking agents) are used and 10 for certa;n intended uses ;t may be advantageous to add plasticisers to the polymerisable compositions according to the invention in order to reduce the brittleness.
H;gh molecular weight plast;c;sers which are known per se, in particular those based on polyurethanes, polycarbonates, 15 polyesters and polyethers, are above all particularly suitable. Polyesters and polyester-carbonates, which are described ;n German Patent Application P 33 16 851.2 are preferred. Examples of possible polymerisable monomers and polymerisation initiators are the compounds mentioned 20 above in connection with the preparation of the 2nd shell of the filler. The polymerisable compositions are parti-cularly suitable for the preparation of shaped dental articles, and also as bone cements and for other ortho-paedic surfaces.
25 Example 1 19.8 kg of methylene chloride and 3.8 kg of highly d;sperse s;l;con d;ox;de (part;cle size about 20 nm~ BET
surface area 50 m2/g) are weighed into a 40 litre stirred autoclave which can be heated, and the stirrer 30 speed is adjusted to 400 rpm. 760 g of y methacryloxy-propyltr;methoxysilane, 980 g of deionised water and 10.4 9 of methacrylic acid are mixed in a separate gl355 vessel.
As soon as the mixture ;s a single phase system (after about 4n minutes at room temperature ;t ;s added in one 35 portion to the st;rred autoclave. The temperature in the stirred autoclave is kept at 40C for 20 hours, and Le A 22 7û1 .
123~399~;
0.38 kg of methyl methacrylatet 0.38 kg of isobutyl methacrylate, 8 g of ethyLene d;methacrylate 3nd 2~ 9 of azoisobutyrodinitrile are then added, a pressure of 5 bar of N2 is applied and the temperature is kept a 70C for 5 3 hours and then at 80C for a further 3 hours. After cooling, the dispersion is diluted with 10 kg of methylene chloride and subjected to a spray-drying process. 5.1 kg of fine-particled filler are obtained.
Example 2 1û Example 1 is repeated, the following amounts being used: 19.8 kg of methylene chlor;de, 3r8 kg of highly d;s-perse silicon dioxide (particle size about 20 nm, BET
surface area 50 m2/g), 456 9 of methacryloxypropyltri-methoxysilane, 588 9 of deionised water, 6 g of methacrylic 15 acid, 550 9 of methyl methacrylate, 11 g of ethylene di-methacrylate and 20 9 of azoisobutyrodinitrile. 4.8 kg of fine-particled filler are obtained.
Example 3 65 g of bisphenol A diglycidyl dimethacrylate, 20 35 9 of triethylene glycol dimethacrylate~ 318 9 of the fine-particled filler of Example 1, 2 g of dibenzoyl per-oxide and small amounts (< 0.1 9) of customary pigments are kneaded to a paste in a kneader. To produce teeth, this paste is pressecl into mouLds and hardened at 130C in 25 the course of 6 m;nutes. The result;ng teeth are distin-guished by be;ng very hard and having a high abrasion resistance.
Example 4 75 g of methyl methacrylate, 20 9 of ethylene 30 dimethacrylate, 5 9 of a polyester containing polycarbon-ate groups (Example 3 of DE-OS tGerman Published Specific-ation) 2,732,718), 20 9 of diben~oyl peroxide, 30 9 of polymethyl-methacrylate bead polymer (d50: 45 ~Im~ Clz ]
in CHCl3: 1.8 dl/g) and 220 9 of fine-particled filler 35 from ExampLe Z are kneaded to a paste~like composition in a kneader. This compos;tion ;s act;vated w;th 2 g of Le 22 701 ~a~3~
_ 9 _ d;benzoyl peroxide and coloured the colour of teeth w;th the customary pigments. After a maturing time of 30 min-utes, the composit;on ;s pressed into teeth moulds and hardened at 120C for 8 minutes. The resulting teeth S are dist;ngu;shed by be;ng very hard and hav;ng a high abras;on res;stance.
Le A 22 7Q1
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A filler for a polymerisable composition comprising an inorganic core, a first shell of vinylsilane and a second shell of (meth)acrylate polymers, characterised in that the in-organic core comprises particles with a particle size of 10 to 500 nm.
2. A filler according to Claim 1 wherein the first shell makes up 2 - 40% by weight, (based on the inorganic core).
3. Filler according to Claim 1,wherein the second shell makes up 3 - 100 % by weight, (based on the inorganic core).
4. A filler according to Claim 1, 2 or 3,wherein the first shell makes up 5 - 25% by weight (based on the inorganic core).
5. A filler according to Claim 1, 2 or 3,wherein the second shell makes up 10 - 50% by weight (based on the inorganic core).
6. A filler according to Claim 1, 2 or 3, wherein the inorganic core is silicon dioxide, a silicate or aluminium oxide.
7. A filler according to Claim 1, 2 or 3, wherein the inorganic core is silicon dioxide or aluminium oxide with a particle size of 10 to 40 nm which has been obtained by flame hydrolysis.
8. A filler according to Claim 1, 2 or 3, wherein the BET surface area of the inorganic core is 30 to 300 m2/g.
9. A filler according to Claim 1, 2 or 3, wherein the BET surface area of the inorganic core is 40 to 200 m2/g.
10. A filler according to Claim 1, 2 or 3, wherein the second shell is crosslinked.
11. A process for preparing a filler according to Claim 1, comprising dispersing inorganic particles with a particle size of 10 to 500 nm in an organic solvent and, in a first step, silanising the particles with a reactive mixture of vinylsilane and water and, in a second step, encasing the product with a (meth)acrylate polymer by polymerisation.
12. A process according to Claim 11, wherein the first shell makes up 2 - 40% by weight, (based on the inorganic core).
13. A process according to Claim 11, wherein the second shell makes up 3 - 100% by weight, (based on the inorganic core).
14. A process according to Claim 11, 12 or 13, wherein the filler is isolated from the solvent by a spray-drying process.
15. A polymerisable composition comprising 20 to 65% by weight of a polymerisable monomer and 10 to 75% by weight of an inorganic-organic filler wherein at least a proportion of the filler is a filler according to Claim 1, 2 or 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833341888 DE3341888A1 (en) | 1983-11-19 | 1983-11-19 | INORGANIC-ORGANIC FILLERS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN POLYMERIZABLE MEASURES |
| DEP3341888.8 | 1983-11-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1238996A true CA1238996A (en) | 1988-07-05 |
Family
ID=6214759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000468012A Expired CA1238996A (en) | 1983-11-19 | 1984-11-16 | Inorganic-organic fillers, a process for their preparation and their use in polymerisable compositions |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4617327A (en) |
| EP (1) | EP0142784B1 (en) |
| JP (2) | JPS60120703A (en) |
| AT (1) | ATE32090T1 (en) |
| CA (1) | CA1238996A (en) |
| DE (2) | DE3341888A1 (en) |
Families Citing this family (56)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3341888A1 (en) * | 1983-11-19 | 1985-05-30 | Bayer Ag, 5090 Leverkusen | INORGANIC-ORGANIC FILLERS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN POLYMERIZABLE MEASURES |
| KR890003069B1 (en) * | 1985-06-10 | 1989-08-21 | 구레하 가가꾸 고오교오 가부시끼가이샤 | Implant material |
| GB8524152D0 (en) * | 1985-10-01 | 1985-11-06 | Cole Polymers Ltd | Bone cement |
| DE3642212A1 (en) * | 1986-12-10 | 1988-06-23 | Espe Stiftung | POLYMERIZABLE MEASURES, METHOD FOR THEIR PRODUCTION AND THEIR USE AS DENTAL MEASURES |
| US4781940A (en) * | 1987-06-26 | 1988-11-01 | Johnson & Johnson Consumer Products, Inc. | Method for producing filler for microfilled dental composite material |
| JP2690364B2 (en) * | 1989-08-09 | 1997-12-10 | 株式会社クラレ | Surface treatment method of inorganic filler for dental materials |
| DE3929422A1 (en) * | 1989-09-05 | 1991-03-07 | Merck Patent Gmbh | POLYMER-COVERED LABEL-SHAPED SUBSTRATES |
| JPH0418453A (en) * | 1990-05-10 | 1992-01-22 | Kuraray Co Ltd | Organic-inorganic composite powder and production of the same powder |
| US6080801A (en) * | 1990-09-13 | 2000-06-27 | Klaus Draenert | Multi-component material and process for its preparation |
| DE4030727A1 (en) * | 1990-09-28 | 1992-04-02 | Eckart Standard Bronzepulver | ARTICULATED METAL PIGMENTS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| US5269980A (en) * | 1991-08-05 | 1993-12-14 | Northeastern University | Production of polymer particles in powder form using an atomization technique |
| US5334626A (en) * | 1992-07-28 | 1994-08-02 | Zimmer, Inc. | Bone cement composition and method of manufacture |
| DE4306153A1 (en) * | 1993-02-27 | 1994-09-01 | Hoechst Ag | Sealable oriented polyolefin multilayer film, process for its production and its use |
| FR2711372B1 (en) * | 1993-10-20 | 1995-12-08 | Atochem Elf Sa | Mineral particles coated with elastomer, process for their preparation, their use for the reinforcement of thermoplastic polymers and said reinforced polymers. |
| US5683501A (en) * | 1993-11-09 | 1997-11-04 | Nippon Shokubai Co., Ltd. | Compound fine particles and composition for forming film |
| DE4402890A1 (en) * | 1994-02-01 | 1995-08-03 | Basf Ag | Process for the production of compositions containing metal particles in the nanometer size range |
| JP3519119B2 (en) * | 1994-05-12 | 2004-04-12 | 日本エヌエスシー株式会社 | Aqueous coating composition and method for producing the same |
| US5726235A (en) * | 1994-05-12 | 1998-03-10 | National Starch And Chemical Investment Holding Corporation | Aqueous coating composition and its preparation |
| US5498781A (en) * | 1994-05-23 | 1996-03-12 | Basf Corporation | Passification of optically variable pigment and waterborne coating compositions containg the same |
| US5795922A (en) * | 1995-06-06 | 1998-08-18 | Clemson University | Bone cement composistion containing microencapsulated radiopacifier and method of making same |
| US6063830A (en) * | 1996-12-06 | 2000-05-16 | Kabushiki Kaisha Shofu | Dental curable composition and artificial tooth |
| CA2233150A1 (en) * | 1997-03-31 | 1998-09-30 | Kuraray Co., Ltd. | Resinous composition for dental use |
| US6693143B2 (en) | 1997-10-03 | 2004-02-17 | Dentsply Detrey Gmbh | Dental materials having a nanoscale filler |
| AU752003B2 (en) | 1997-10-03 | 2002-09-05 | Dentsply International Inc. | Dental materials having a nanoscale filler |
| US6020395A (en) * | 1998-01-06 | 2000-02-01 | Kerr Corporation | Homogeneous microfilled dental composite material and method of preparation |
| JP2000080013A (en) * | 1998-09-02 | 2000-03-21 | Gc Corp | Restorative dental material composition |
| US6689823B1 (en) * | 1999-03-31 | 2004-02-10 | The Brigham And Women's Hospital, Inc. | Nanocomposite surgical materials and method of producing them |
| US6572693B1 (en) | 1999-10-28 | 2003-06-03 | 3M Innovative Properties Company | Aesthetic dental materials |
| US6376590B2 (en) | 1999-10-28 | 2002-04-23 | 3M Innovative Properties Company | Zirconia sol, process of making and composite material |
| US6387981B1 (en) | 1999-10-28 | 2002-05-14 | 3M Innovative Properties Company | Radiopaque dental materials with nano-sized particles |
| CA2387215C (en) | 1999-10-28 | 2010-02-09 | 3M Innovative Properties Company | Dental materials with nano-sized silica particles |
| US6730156B1 (en) | 1999-10-28 | 2004-05-04 | 3M Innovative Properties Company | Clustered particle dental fillers |
| DE10005036A1 (en) * | 2000-02-04 | 2001-08-09 | Bayer Ag | Non-aqueous polymer suspension, for shock- and vibration-damping applications, e.g. in sports equipment, contains spherical, monodisperse vinyl polymer and carrier liquid |
| EP1195416A3 (en) * | 2000-10-05 | 2005-12-28 | Degussa AG | Polymerisable silicone-organic nanocapsules |
| EP1199336B1 (en) | 2000-10-21 | 2014-01-15 | Evonik Degussa GmbH | Functionalized, structure modified silicic acids |
| ATE496098T1 (en) * | 2000-10-21 | 2011-02-15 | Evonik Degussa Gmbh | RADIATION CURING PAINT SYSTEMS |
| DE50016050D1 (en) | 2000-10-21 | 2011-02-03 | Evonik Degussa Gmbh | Functionalized silicic acids |
| CA2473861C (en) | 2002-01-31 | 2012-03-13 | 3M Innovative Properties Company | Dental pastes, dental articles, and methods |
| US20050202178A1 (en) | 2002-05-02 | 2005-09-15 | Hussmann Corporation | Merchandisers having anti-fog coatings and methods for making the same |
| US20030205059A1 (en) * | 2002-05-02 | 2003-11-06 | Hussmann Corporation | Merchandisers having anti-fog coatings and methods for making the same |
| DE10335181B4 (en) * | 2003-07-30 | 2011-01-13 | Heraeus Kulzer Gmbh | Artificial teeth with high abrasion resistance in enamel or cutting area |
| JP4951846B2 (en) * | 2004-07-20 | 2012-06-13 | セイコーエプソン株式会社 | Ink composition |
| DE102005000824A1 (en) * | 2005-01-05 | 2006-07-13 | Consortium für elektrochemische Industrie GmbH | Nanoparticle-containing organocopolymers |
| JP2007038643A (en) * | 2005-06-29 | 2007-02-15 | Oji Paper Co Ltd | Composite fine particle, dispersion liquid, method of producing dispersion liquid, inkjet recording body and method of producing inkjet recording body |
| JP5188045B2 (en) * | 2006-08-30 | 2013-04-24 | キヤノン株式会社 | Nano-oxide particles and method for producing the same |
| JP5247016B2 (en) * | 2006-08-31 | 2013-07-24 | キヤノン株式会社 | Method for producing composite material and dispersant |
| US8647426B2 (en) | 2006-12-28 | 2014-02-11 | 3M Innovative Properties Company | Dental filler and methods |
| EP2110389A1 (en) * | 2008-04-18 | 2009-10-21 | Nanoresins AG | Polymerisable substance with connected nanoparticles |
| WO2010045105A1 (en) * | 2008-10-15 | 2010-04-22 | 3M Innovative Properties Company | Fillers and composite materials with zirconia and silica nanoparticles |
| GB2466251B (en) * | 2008-12-16 | 2011-03-09 | Ind Tech Res Inst | Encapsulant compositions and method for fabricating encapsulant materials |
| US8834845B2 (en) * | 2009-04-02 | 2014-09-16 | Innotere Gmbh | Bioactive bone cement and method for its production |
| DE102011003289A1 (en) | 2011-01-27 | 2012-08-02 | Voco Gmbh | Dental provisional superstructures as well as materials for their production and corresponding methods |
| KR101952463B1 (en) * | 2011-02-21 | 2019-02-26 | 아사히 가세이 케미칼즈 가부시키가이샤 | Coating material containing organic/inorganic composite, organic/inorganic composite film and antireflection member |
| EP2604247A1 (en) * | 2011-12-15 | 2013-06-19 | Dentsply DeTrey GmbH | Composite filler particles and process for the preparation thereof |
| JP6161733B2 (en) * | 2014-01-31 | 2017-07-12 | 株式会社ジーシー | Dental glass ionomer cement filler and method for producing the same |
| US9670376B1 (en) * | 2016-07-18 | 2017-06-06 | Advenira Enterprises, Inc. | Hybrid sol-gel coating materials and coatings and methods of forming and using thereof |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3258444A (en) * | 1964-07-31 | 1966-06-28 | Owens Illinois Glass Co | Glass base coated with an acid hydrolyzed polysilanol, the method of coating, the coating composition, and the method of preparing the composition |
| US3471439A (en) * | 1966-03-10 | 1969-10-07 | Amicon Corp | Reinforcing filler |
| US3503128A (en) * | 1966-03-21 | 1970-03-31 | Dentsply Int Inc | Dental filling composition of a coefficient of thermal expansion approximating that of natural tooth enamel |
| US3505279A (en) * | 1966-10-27 | 1970-04-07 | Owens Corning Fiberglass Corp | Polyolefin-organosilane graft polymers |
| US3578629A (en) * | 1968-05-21 | 1971-05-11 | Monsanto Co | Process for preparing reinforced polyolefins |
| GB1278413A (en) * | 1968-07-23 | 1972-06-21 | Dental Fillings Ltd | Direct filling composition for teeth and novel filler for use therein |
| US3897586A (en) * | 1970-08-05 | 1975-07-29 | Du Pont | Polymer coated pigment particles and a process for their preparation |
| ZA722919B (en) * | 1971-05-24 | 1973-02-28 | Lee Pharmaceuticals | Stable silanol compositions and process for making them |
| US4028325A (en) * | 1972-08-09 | 1977-06-07 | King Alan G | Composite dental material and method of preparing same |
| DE2405578B2 (en) * | 1974-02-06 | 1976-01-08 | Kulzer & Co Gmbh, 6380 Bad Homburg | Dental material containing polymerizable binding agent and its use for teeth and tooth replacement parts |
| DE2850917A1 (en) * | 1978-11-24 | 1980-06-04 | Bayer Ag | DENTAL MATERIALS BASED ON ORGANIC PLASTICS IN PASTOESE FORM |
| DE2850918A1 (en) * | 1978-11-24 | 1980-06-04 | Bayer Ag | ROENTGENOPAKE DENTAL MATERIALS BASED ON ORGANIC PLASTICS IN PASTOESE FORM |
| DE2938875A1 (en) * | 1979-09-26 | 1981-04-23 | Bayer Ag, 5090 Leverkusen | DENTAL MATERIALS BASED ON ORGANIC PLASTICS IN PASTOESE FORM |
| US4368235A (en) * | 1980-01-18 | 1983-01-11 | General Electric Co. | Silicone resin coating composition |
| DE3034374A1 (en) * | 1980-09-12 | 1982-08-19 | DMG Dental-Material GmbH, 2000 Hamburg | MINERAL PARTICLES |
| US4421660A (en) * | 1980-12-15 | 1983-12-20 | The Dow Chemical Company | Colloidal size hydrophobic polymers particulate having discrete particles of an inorganic material dispersed therein |
| DE3170993D1 (en) * | 1981-03-24 | 1985-07-25 | Blendax Werke Schneider Co | Dental filling material |
| DE3379203D1 (en) * | 1982-07-14 | 1989-03-23 | Battelle Development Corp | Method for producing cross-linked resin coatings on substrates |
| US4442240A (en) * | 1983-07-14 | 1984-04-10 | Bisco, Inc. | Dental filling materials |
| DE3341888A1 (en) * | 1983-11-19 | 1985-05-30 | Bayer Ag, 5090 Leverkusen | INORGANIC-ORGANIC FILLERS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN POLYMERIZABLE MEASURES |
| JPH0477022A (en) * | 1990-07-16 | 1992-03-11 | Ricoh Co Ltd | Receiver for spread spectrum communication system |
-
1983
- 1983-11-19 DE DE19833341888 patent/DE3341888A1/en not_active Withdrawn
-
1984
- 1984-11-08 EP EP84113506A patent/EP0142784B1/en not_active Expired
- 1984-11-08 AT AT84113506T patent/ATE32090T1/en active
- 1984-11-08 DE DE8484113506T patent/DE3468894D1/en not_active Expired
- 1984-11-15 JP JP59239601A patent/JPS60120703A/en active Granted
- 1984-11-16 CA CA000468012A patent/CA1238996A/en not_active Expired
-
1985
- 1985-10-10 US US06/786,256 patent/US4617327A/en not_active Expired - Lifetime
-
1991
- 1991-11-06 JP JP3317389A patent/JPH05105707A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE3341888A1 (en) | 1985-05-30 |
| JPS60120703A (en) | 1985-06-28 |
| JPH0477022B2 (en) | 1992-12-07 |
| JPH05105707A (en) | 1993-04-27 |
| EP0142784B1 (en) | 1988-01-20 |
| US4617327A (en) | 1986-10-14 |
| EP0142784A1 (en) | 1985-05-29 |
| ATE32090T1 (en) | 1988-02-15 |
| DE3468894D1 (en) | 1988-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1238996A (en) | Inorganic-organic fillers, a process for their preparation and their use in polymerisable compositions | |
| EP0368657B1 (en) | Dental restorative material | |
| US4374937A (en) | Dispersions of siliceous solids in liquid organic media | |
| CA1149537A (en) | Dental materials based on organic plastics in paste form | |
| CA2008895C (en) | Dental filling material | |
| US5548001A (en) | Swellable bead polymer containing fillers | |
| US4389497A (en) | Use of agglomerates of silicic acid as fillers in dental materials | |
| US4302376A (en) | Dental materials which are opaque to X-rays and are based on organic plastics in paste form | |
| CA2267747A1 (en) | Radically polymerizable dental material | |
| US4826901A (en) | Curable casting resins | |
| EP0534753B1 (en) | Composite composition having high transparency and process for producing same | |
| US5391647A (en) | Composite composition having high transparency and process for producing same | |
| CA1290486C (en) | Method for making curable casting resins | |
| JPS58125709A (en) | Crosslinked and filler-containing bead polymer and manufacture | |
| US4880887A (en) | Method for curing dental resins | |
| JP3442430B2 (en) | Casting resin-suspension and molded body composed thereof | |
| JP3859737B2 (en) | Dental composite material | |
| JPH10504058A (en) | Reaction curable composition and solid surface material | |
| JPH046648B2 (en) | ||
| WO1990001470A1 (en) | Simulated colored granite and process | |
| CN85101839A (en) | Inorganic-organic filler, its preparation method and the application in polymeric composition thereof | |
| JPH04210609A (en) | Production of composite material for dental use | |
| JP3538982B2 (en) | Resin particles for FRP and FRP composition | |
| JPH0549704B2 (en) | ||
| JPH0157082B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |