WO1997014674A1 - Liquid crystalline (meth)acrylate compounds, composition and method - Google Patents
Liquid crystalline (meth)acrylate compounds, composition and method Download PDFInfo
- Publication number
- WO1997014674A1 WO1997014674A1 PCT/US1996/016436 US9616436W WO9714674A1 WO 1997014674 A1 WO1997014674 A1 WO 1997014674A1 US 9616436 W US9616436 W US 9616436W WO 9714674 A1 WO9714674 A1 WO 9714674A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon atoms
- substituted
- unsubstituted
- moiety
- independently
- Prior art date
Links
- 0 *CC(CON)O Chemical compound *CC(CON)O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/708—Ethers
- C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/50—Preparations specially adapted for dental root treatment
- A61K6/54—Filling; Sealing
-
- 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
-
- 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
- A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- A61K6/893—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/061—Polyesters; Polycarbonates
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/064—Polymers containing more than one epoxy group per molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/834—Chemically modified polymers by compounds containing a thiol group
- C08G18/835—Unsaturated polymers modified by compounds containing a thiol group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/10—Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4292—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
- C08L67/07—Unsaturated polyesters having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
- C09K19/2021—Compounds containing at least one asymmetric carbon atom
- C09K19/2028—Compounds containing at least one asymmetric carbon atom containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -COO-CH*-CH3
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
- C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2270/00—Compositions for creating interpenetrating networks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
Definitions
- the invention relates to liquid crystalline (meth)acrylates
- electrooptical application such as in liquid-crystal displays.
- invention provides (meth)acrylate compounds which are liquid below
- compositions for treating natural teeth such as
- the invention provides dental cement
- compositions and methods of using them for binding hard tooth compositions and methods of using them for binding hard tooth
- the cement compositions include
- compositions of the invention are useful as dental
- compositions of the invention are cements, liners, bases and restoratives.
- compositions include less reactive diluent than prior art compositions.
- terephthaloyl ester moiety are disclosed by G.G.Barclay, C.K. Ober,
- a diacrylate (wherein R is H) and a dimethacrylate (wherein R is CH 3 ) having the formula IV which comprises a biphenylhydroxy moiety is disclosed by H. Litt Morton, Wha-Tzong Whang, Kung-Ti Yen, Xue-Jun Qian, in J. Polym. Sci., Part A,: Polym. Chem. 31 (1993) 183, Morton H. Lift US 89-369205.
- Acetylene terminated aromatic ester having the formula V are described by E. P. Douglas, Polymer Prep. 34 (1993) 702.
- Methacrylates having the formula VI with a ridged rod-like moiety are disclosed in T. Shindo, T. Uryu, Liquid Crystals 15 (1993) 239).
- liquid crystalline mono- or difunctional molecules have melting temperatures and liquid crystalline behavior at temperatures above 50°C (Table 1 below, page 25). An application of these molecules in the liquid crystalline phase require temperatures over their melting temperature (50 to 170°C). An application at room temperature is only possible in the solid state or in solution.
- monomers which are liquid at room temperature and which show liquid crystalline behavior at least between 20 and 40°C. These liquid crystalline monomers are useful in dentistry, medicine, microelectronics and optoelectronics.
- R T is a group of the general formula
- each L 1 and L 2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
- R 3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
- R 4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
- M is a mesogenic group of the general formula -A-Z, -A-Y B-Z, -A-Y B-Y 2 -C-Z or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to
- each L and L 2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
- Z is a hydrogen, halogen, CN, -OR, COOR, NO 2 , a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
- X is a covalent bond, CO, NHCO, OCO n is an integer from 1 to 10.
- Figure 1 is a graph of the thermomechanical properties of a
- the invention provides a polymerizable compound within the scope of the general formula:
- each L-, and L 2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN,
- R 3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms,
- R 4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
- each L and L 2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN,
- Z is a hydrogen, halogen, CN, -OR, COOR, NO 2 , a halogen substituted or unsubstituted alkylene or alkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having
- X is a covalent bond, CO, NHCO, OCO and n is an integer from 1 to
- liquid crystalline (meth)acrylates within the scope of general formula 1 which have at least two polymerizable double bonds and at least two rigid rod-like moieties R and M
- each Li and L 2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN R 3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
- R 4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
- M is a mesogenic group of the general formula
- each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms
- each LT and L 2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
- Z is a hydrogen, halogen, CN, -OR, COOR, NO 2 , a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
- X is a covalent bond, CO, NHCO, OCO n is an integer from 1 to 10.
- liquid crystalline (meth)acrylates have structures A and B.
- a macromonomer within the scope of general formula 5 is formed by reaction of a 2,3-epoxypropyl (meth)acrylate compound within the scope of general formula 4, a diphenol compound within the scope of general formula 3 and a diepoxide compound within the scope of general formula 2 as follows.
- R 2 is a group of the general formula
- each L T and L 2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
- R 4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
- R T is a substituted or unsubstituted aryl having from 6 to 24 carbon atoms and/or a substituted or unsubstituted cycloalkyl having from 5 to 12 carbon atoms.
- R ⁇ is
- R 5 is hydrogen, alkyl having from 1 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 18 carbon atoms and
- Y is substituted or unsubstituted alkylene having from 1 to 5 carbon atoms, O, CO, OCO, S, SO 2 and, n is an integer from 1 to 10. Preferably n is 1, 2, or 3.
- R 3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
- M is a mesogenic group of the general formula
- each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms
- each L T and L 2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
- Z is a hydrogen, halogen, CN, -OR, COOR, NO 2 , a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
- esterification, etherification and urethane formation of the di(meth)acrylate hydroxyl groups is carried out in solutions.
- solvents for the esterification were used tetrahydrofurane, dioxane, CH 2 CI 2 , DMF or others, or polymerizable monomers such as triethyleneglycol bismethacrylate, diethyleneglycol bismethacrylate, dioxolan bismethacrylate, vinyl-, vinylene- or vinylidene-, acrylate- or methacrylate substituted spiroorthoesters and 2,2-bis[p- (acryloxyethoxy) phenyl] propane.
- liquid crystalline di(meth)acrylate within the scope of structural formula 9 is synthesized in the following manner: 2,3- epoxy propoxy methacrylate and 4,4 ' -dihydroxy biphenyl are mixed and reacted for 15 hours at 115°C to form a methacrylate terminated macromonomer having hydroxyl groups.
- the macromonomer hydroxyl groups are then esterified by mixing at O 97/14674 PC17US96/16436
- compositions of the invention are formulated as one, two or more components, UV curable, visible light curable, self cure, and/or dual cure product or combinations of these.
- the composition of a preferred embodiment of the invention includes polymerizable carboxylic acid monomer, an optional filler and/or diluent, a cationic elutable glass or other source of polyvalent cations, and a polymerization catalyst system.
- Fillers which are suited for use in compositions of the invention are organic and/or inorganic particles, for example inorganic glasses such as are used in glass ionomer cements.
- Exemplary of such fillers are those of U.S. Patent 4,814,362 which is incorporated herein by reference in its entirety.
- Preferred fillers are glasses formed from or including, barium, calcium, strontium, lanthanum, tantalum, and/or tungsten silicates and aluminates and/or aluminosilicates, silica, including submicron silica, quartz, and/or ceramics for example, calcium hydroxy apatite.
- reactive cations especially those of calcium, strontium and aluminium, and anions especially fluoride ions; are eluted from the fillers.
- the fillers used in the invention preferably are reduced in particle size and are preferably silanated before they are incorporated into such compositions.
- Preferred levels of filler are from about 20% to about 85% based on the total weight of the composition, with from about 40% to about 85% being more preferable and about 50-80% being most preferred. If a more finely particulated filler is used, amounts of filler may be decreased due to the relative increase in surface area which attends the smaller sizes of particles.
- Preferred particle size distributions are from 0.02 to 50 microns, more preferably 0.1 to 10 microns, and most preferably 1 to 6 microns.
- compositions of the present invention may be achieved using standard compounding techniques. For example, liquids, photoinitiator(s), and accelerator(s) are blended first, and fillers are added incrementally thereafter.
- a photosafe room illumination i.e., one that does not contain substantial amounts of wavelengths of electromagnetic radiation that would activate the photoinitiating system is used to avoid initiating polymerization of the composition prematurely.
- the compounds of the present invention also have medical applications such as in self adhesive bone cements. However, they are most preferred to use in dental treatment by application to a tooth or a number of teeth in vivo, in the mouth of a live patient by a dentist or dental practitioner.
- the application of the compositions of the invention is preferably
- ingredients such as curing catalysts, initiators, accelerators, diluents
- composition is applied as a cement using
- Inlays preferably are polymers, or
- inlays are machined from metal such as titanium or gold
- polymer compositions for example by CAD-CAM procedures.
- appliances are bonded to teeth using cement compositions of the
- Such cement compositions join metal or ceramic to tooth by
- a preferred composition of the invention includes a two-part
- One part includes an initiator.
- the second part comprises filled and the co-initiator.
- the two parts are spatuled to form a cement
- the cement includes a visible light and/or a
- luting cement compositions have low
- compositions of the present invention may be prepared of such high
- compositions of the invention are mechanically
- a preferred dental treatment in accordance with the invention is
- the dental filling composition includes finely divided filler.
- composition is applied to a tooth as a filling material
- component pit and fissure sealant which includes at least one
- the invention are an especially valuable means of reducing caries by
- the invention are preferably applied with or without prior acid etching or
- compositions of the invention are preferably included in compositions of the
- Fluoride is eluted to reduce the incidence of caries in tooth
- compositions of the invention include two or more
- the polymerizable monomer is preferably liquid at 23 ' C,
- composition with amounts ranging from about 1 to about 99.98%
- compositions of the invention include an adhesion
- promoter for example a phosphorus-containing adhesion promoter
- the phosphorus derivative may be any halogen atoms covalently or otherwise bonded directly to a phosphorus atom.
- the phosphorus derivative may be any halogen atoms covalently or otherwise bonded directly to a phosphorus atom.
- phosphorus-containing adhesion promoters comprise polymerizable
- phosphorus materials having ethylenic unsaturation include, among others, organic esters of one or more acids of phosphorus
- organic portion of the ester contains at least one polymerizable
- the organic portion of the ester may
- alkenyl alkenoxy, cycloalkenyl, aralkenyl, or alkenaryl
- the organic portion preferably may have from 2 to 40 carbon atoms.
- atoms i.e., atoms other than carbon, and can be unsubstituted or
- phosphoric acid groups such as hydroxyethyl methacrylate
- dimethacrylate phosphate dimethacrylate phosphate.
- Other suitable polymerizable phosphorus acid esters are disclosed, for example, in U.S. Pat. No. 4,499,251 to
- the preferred compounds are those polyethylenically unsaturated
- R is an organic radical having a valency of n +1; and R may be
- unsubstituted and may comprise an aliphatic radical, or a
- R 1 is a hydrogen atom, alkyl having from 1 to 3 carbon atoms,
- n is an integer of at least 1.
- n is an integer of 2 or
- pentaerythritol trimethacrylate monophosphate dipentaerythritol pentaacrylate monophosphate
- dipentaerythritol pentaacrylate monophosphate dipentaerythritol
- acid compound may comprise from about 0.25 to about 99.998% by
- phosphorus acid compound would comprise from about 2 to about
- compositions of the invention include a catalyst
- the catalyst may comprise, for example,
- an organic peroxide type initiator such as dibenzoyl
- an actinic light sensitive initiator such as ultraviolet light-
- benzophenones benzoin methyl ether, isopropoxybenzoin, benzoin
- alpha-diketones such as camphoroquinone
- the preferred initiators are the visible light sensitive initiators.
- the catalyst generally is employed in the range of
- the catalyst is used within the range of from 0.01 to about
- compositions which include an accelerator system
- the amine or amine salt may be
- composition whereas the sulfinic acid or salt thereof is present in an
- amine or amine salt is in the range of 0.001 to about 10% by weight of
- the polymerizable composition and the sulfinic acid or a sulfinic acid
- salt is in the range from about 0.01 to about 5 percent by weight of the
- the amine or amine salt is in an amount from about 0.1-8 percent by
- this invention desirably is a secondary or tertiary amine rather than a
- Suitable amines include
- Primers and adhesives of the invention may be filled to such an
- composition of the invention comprises by weight about 5-20%
- Example 1 To 5.00 g liquid crystalline di(meth)acrylate of Example 1 are added and 0,05 g JRAGCURE 651 (Ciba - Geigy). Using a curing unit (Dentsply De Trey) the mixture is polymerized by irradiation with visible light during 40 seconds. The degree of polymerization is about 85 %. The obtained material shows a volume shrinkage of 2.4 percent.
- the thermo-mechanical properties are shown in Figure 1 wherein E' (storage modulus) is 2.8 • 10 9 Ps (25°C), E" (loss modulus) is 2.9 • 10 8 Pa (25°C) and tan ⁇ (E'VE') is 0.22.
- Table 1 shows the Melting Points (°C) of LC-Monomers II - VI and the glass transition temperatures of Examples 1 and 2.
- the powder and liquid are mixed in a 1 :1 ratio by volume to form a
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP51590897A JP2001509128A (en) | 1995-10-17 | 1996-10-16 | Liquid crystal (meth) acrylate compounds, compositions and methods |
DE69618661T DE69618661T2 (en) | 1995-10-17 | 1996-10-16 | LIQUID CRYSTALINE (METH) ACRYLATE COMPOUNDS, COMPOSITION AND METHOD THEREFOR |
EP96936465A EP0861230B1 (en) | 1995-10-17 | 1996-10-16 | Liquid crystalline (meth)acrylate compounds, composition and method |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US54395095A | 1995-10-17 | 1995-10-17 | |
US08/723,443 | 1996-10-07 | ||
US08/543,950 | 1996-10-07 | ||
US08/723,443 US5998499A (en) | 1994-03-25 | 1996-10-07 | Liquid crystalline (meth)acrylate compounds, composition and method |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997014674A1 true WO1997014674A1 (en) | 1997-04-24 |
Family
ID=27067464
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1996/016436 WO1997014674A1 (en) | 1995-10-17 | 1996-10-16 | Liquid crystalline (meth)acrylate compounds, composition and method |
Country Status (6)
Country | Link |
---|---|
US (2) | US5998499A (en) |
EP (1) | EP0861230B1 (en) |
JP (1) | JP2001509128A (en) |
CA (1) | CA2229379A1 (en) |
DE (1) | DE69618661T2 (en) |
WO (1) | WO1997014674A1 (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1121269A (en) * | 1997-06-30 | 1999-01-26 | Dainippon Ink & Chem Inc | Liquid-crystal (meth)acrylate compound, liquid-crystal composition, and optical an isotropic body using the same compound |
US6258974B1 (en) | 1993-04-13 | 2001-07-10 | Southwest Research Institute | Metal oxide compositions composites thereof and method |
US6417244B1 (en) | 1993-04-13 | 2002-07-09 | Southwest Research Institute | Metal oxide compositions and methods |
US6695617B1 (en) | 1993-04-13 | 2004-02-24 | Southwest Research Institute | Methods of dental repair using functionalized nanoparticles |
US7094358B2 (en) | 2001-03-07 | 2006-08-22 | The University Of Texas System | Ultra-low shrinkage composite resins based on blended nematic liquid crystal monomers |
US7108801B2 (en) | 2001-01-23 | 2006-09-19 | Southwest Reasearch Institute | Methods and blends for controlling rheology and transition temperature of liquid crystals |
US8415484B2 (en) | 2008-08-27 | 2013-04-09 | Arena Pharmaceuticals, Inc. | Substituted tricyclic acid derivatives as S1P1 receptor agonists useful in the treatment of autoimmune and inflammatory disorders |
US8580841B2 (en) | 2008-07-23 | 2013-11-12 | Arena Pharmaceuticals, Inc. | Substituted 1,2,3,4-tetrahydrocyclopenta[b]indol-3-yl)acetic acid derivatives useful in the treatment of autoimmune and inflammatory disorders |
US8853419B2 (en) | 2010-01-27 | 2014-10-07 | Arena Pharmaceuticals, Inc. | Processes for the preparation of (R)-2-(7-(4-cyclopentyl-3-(trifluoromethyl)benzyloxy)-1,2,3,4-tetrahydrocyclopenta[b]indol-3-yl)acetic acid and salts thereof |
US9085581B2 (en) | 2010-03-03 | 2015-07-21 | Arena Pharmaceuticals, Inc. | Processes for the preparation of S1P1 receptor modulators and crystalline forms thereof |
US10301262B2 (en) | 2015-06-22 | 2019-05-28 | Arena Pharmaceuticals, Inc. | Crystalline L-arginine salt of (R)-2-(7-(4-cyclopentyl-3-(trifluoromethyl)benzyloxy)-1,2,3,4-tetrahydrocyclo-penta [b]indol-3-yl)acetic acid(Compund1) for use in SIPI receptor-associated disorders |
US11007175B2 (en) | 2015-01-06 | 2021-05-18 | Arena Pharmaceuticals, Inc. | Methods of treating conditions related to the S1P1 receptor |
US11478448B2 (en) | 2017-02-16 | 2022-10-25 | Arena Pharmaceuticals, Inc. | Compounds and methods for treatment of inflammatory bowel disease with extra-intestinal manifestations |
US11534424B2 (en) | 2017-02-16 | 2022-12-27 | Arena Pharmaceuticals, Inc. | Compounds and methods for treatment of primary biliary cholangitis |
US11555015B2 (en) | 2018-09-06 | 2023-01-17 | Arena Pharmaceuticals, Inc. | Compounds useful in the treatment of autoimmune and inflammatory disorders |
Families Citing this family (41)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6194481B1 (en) | 1999-05-19 | 2001-02-27 | Board Of Regents Of The University Of Texas System | Mechanically strong and transparent or translucent composites made using zirconium oxide nanoparticles |
CA2411464A1 (en) * | 2000-06-13 | 2001-12-20 | Dentsply International Inc. | Low shrinking polymerizable dental material |
US20040199004A1 (en) * | 2001-01-23 | 2004-10-07 | Southwest Research Institute | Novel mesogens |
US7147800B2 (en) * | 2001-01-23 | 2006-12-12 | Southwest Research Institute | Selective ether cleavage synthesis of liquid crystals |
DE60228846D1 (en) * | 2001-07-09 | 2008-10-23 | Southwest Res Inst | NEW MESOGENES, METHOD FOR THEIR PRODUCTION AND USE |
FR2828090B1 (en) * | 2001-08-03 | 2003-11-21 | Andre Benhamou | IMPLANT FOR DENTAL OR SIMILAR USE, CONSISTING OF A CORE AND A CERAMIC SLEEVE CONNECTED TO ONE ANOTHER BY GLUE |
JP4368140B2 (en) * | 2002-08-19 | 2009-11-18 | 尚武 中村 | Liquid crystalline compound and electrorheological fluid using the same |
US6837712B2 (en) * | 2002-08-23 | 2005-01-04 | Kerr Corporation | Dental restorative compositions |
US7037965B2 (en) * | 2002-08-27 | 2006-05-02 | Acushnet Company | Golf balls comprising glass ionomers, ormocers, or other hybrid organic/inorganic compositions |
US7238122B2 (en) * | 2002-08-27 | 2007-07-03 | Acushnet Company | Ormocer composites for golf ball components |
US6793592B2 (en) * | 2002-08-27 | 2004-09-21 | Acushnet Company | Golf balls comprising glass ionomers, or other hybrid organic/inorganic compositions |
DE10242106A1 (en) * | 2002-09-11 | 2004-04-15 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Phosphorus-containing carboxylic acid derivatives with organic polymerizable groups |
US20040209990A1 (en) * | 2003-04-15 | 2004-10-21 | Uwe Walz | Low shrinking polymerizable dental material |
GB2418671B (en) * | 2003-07-12 | 2007-11-14 | Merck Patent Gmbh | Polymerised liquid crystal film with improved adhesion |
JP2007515547A (en) * | 2003-12-22 | 2007-06-14 | ダウ グローバル テクノロジーズ インコーポレイティド | Accelerated organoborane amine complex-initiated polymerizable composition |
US8501886B2 (en) * | 2003-12-22 | 2013-08-06 | Dow Global Technologies Llc | Accelerated organoborane amine complex initiated polymerizable compositions |
JP4539108B2 (en) * | 2004-02-16 | 2010-09-08 | Dic株式会社 | Polymerizable compound and polymerizable composition |
CA2570341C (en) * | 2004-06-15 | 2012-12-18 | Dentsply International Inc. | Radical polymerizable macrocyclic resin compositions with low polymerization stress |
CA2571207C (en) * | 2004-06-15 | 2014-08-05 | Dentsply International Inc. | Low shrinkage and low stress dental compositions |
EP1690915B1 (en) * | 2005-02-14 | 2008-03-26 | MERCK PATENT GmbH | Mesogenic compounds, liquid crystal medium and liquid crystal display |
US20080287566A1 (en) * | 2005-09-28 | 2008-11-20 | Essential Dental Systems, Inc. | Epoxy based oil free root canal sealer |
WO2007044730A1 (en) * | 2005-10-07 | 2007-04-19 | Dow Global Technologies Inc. | Amido-organoborate initiator systems |
CN101351182B (en) * | 2005-12-29 | 2016-01-20 | 3M创新有限公司 | Dental composition and the initiator system with polycyclic aromatic component |
US20080076848A1 (en) * | 2006-06-09 | 2008-03-27 | Xiaoming Jin | Low stress flowable compositions |
US7524907B2 (en) * | 2006-10-12 | 2009-04-28 | Dow Global Technologies, Inc. | Accelerated organoborane initiated polymerizable compositions |
US20080103274A1 (en) * | 2006-10-12 | 2008-05-01 | Jialanella Gary L | Accelerated organoborane initiated polymerizable compositions |
US20080221291A1 (en) | 2007-03-07 | 2008-09-11 | 3M Innovative Properties Company | Microstructured optical films comprising biphenyl difunctional monomers |
BRPI0913521A2 (en) * | 2008-09-04 | 2015-10-13 | 3M Innovative Properties Co | hardening dental composition and dental article |
EP2376573B1 (en) * | 2008-10-22 | 2019-12-18 | 3M Innovative Properties Company | Dental composition comprising biphenyl di(meth)acrylate monomer comprising urethane moieties |
ES2540232T3 (en) | 2009-07-08 | 2015-07-09 | Dermira (Canada), Inc. | TOFA analogues useful in the treatment of dermatological disorders or conditions |
DE102009059104A1 (en) * | 2009-12-18 | 2011-06-22 | Johannes-Gutenberg-Universität Mainz, 55122 | Functional branched polyether copolymers and process for their preparation |
JP5908795B2 (en) * | 2012-05-31 | 2016-04-26 | 日立オムロンターミナルソリューションズ株式会社 | Easy-release adhesive, adhesive material using the same, and processing apparatus |
CN103351872B (en) * | 2013-06-20 | 2016-02-03 | 深圳市华星光电技术有限公司 | For the Liquid Crystalline Polymeric Materials of liquid-crystal display frame, frame and manufacture method |
TWI662020B (en) * | 2014-10-03 | 2019-06-11 | 日商迪愛生股份有限公司 | Epoxy ester compound, cellulose ester resin composition, optical film and liquid crystal display device |
JP2016110152A (en) | 2014-12-08 | 2016-06-20 | 三星電子株式会社Samsung Electronics Co.,Ltd. | Reflection-proof film and organic light emission device comprising the same |
KR101623086B1 (en) | 2014-12-08 | 2016-05-20 | 삼성전자 주식회사 | Antireflection film and organic light emitting device provided with the same |
WO2018096725A1 (en) * | 2016-11-28 | 2018-05-31 | 東洋ゴム工業株式会社 | Photocrosslinkable liquid crystalline polymer |
US11174217B2 (en) | 2017-06-12 | 2021-11-16 | Dic Corporation | Polymerizable compound and liquid crystal composition |
CN111194305B (en) | 2017-11-17 | 2023-01-03 | Dic株式会社 | Polymerizable compound, and liquid crystal composition and liquid crystal display element using same |
JP6729815B2 (en) | 2018-03-01 | 2020-07-22 | Dic株式会社 | Polymerizable compound, liquid crystal composition using the same, and liquid crystal display device |
EP3721858B1 (en) * | 2019-04-11 | 2022-02-16 | Dentsply DeTrey GmbH | Dental composition |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0379058A2 (en) * | 1989-01-17 | 1990-07-25 | The Dow Chemical Company | Vinyl ester resins containing mesogenic/rigid rodlike moieties |
EP0675186A1 (en) * | 1994-03-30 | 1995-10-04 | F. Hoffmann-La Roche AG | Photo-curable liquid crystals |
Family Cites Families (230)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US150262A (en) * | 1874-04-28 | Improvement in caps for glass syringes | ||
CA817442A (en) | 1969-07-08 | M. Samour Carlos | Polymerizable monomers, copolymers thereof and adhesive made therefrom | |
CA563464A (en) | 1958-09-16 | General Electric Company | Oxygenated polymerizable acrylic acid type esters and methods of preparing and polymerizing the same | |
US212975A (en) * | 1879-03-04 | Improvement in syringes | ||
US543829A (en) * | 1895-07-30 | Isaac q | ||
CA878006A (en) | 1971-08-10 | Ii Henry L. Lee | Dental filling material | |
US173850A (en) * | 1876-02-22 | Improvement in syringes | ||
DE277689C (en) | 1900-01-01 | |||
DE229140C (en) | 1908-02-25 | 1910-12-02 | ||
SU52106A1 (en) | 1937-02-17 | 1937-11-30 | Ю.Ю. Лурье | Compression Tester |
DE1003448B (en) | 1953-03-28 | 1957-02-28 | Degussa | Process for the preparation of polymerization products |
US3066112A (en) * | 1959-01-30 | 1962-11-27 | Rafael L Bowen | Dental filling material comprising vinyl silane treated fused silica and a binder consisting of the reaction product of bis phenol and glycidyl acrylate |
US3150801A (en) * | 1960-09-06 | 1964-09-29 | Clark H Hamilton | Syringe |
US3200142A (en) * | 1963-02-01 | 1965-08-10 | Rafael L Bowen | Surface-active comonomer and method of preparation |
US3327017A (en) * | 1963-10-03 | 1967-06-20 | Japan Gas Chemical Co | Molding composition comprising a thermosetting aromatic hydrocarbon-aldehyde-phenol resin and a thermoplastic linear polymer |
NL128018C (en) * | 1963-12-11 | |||
US3327016A (en) * | 1964-07-09 | 1967-06-20 | Epoxylite Corp | Epoxide compositions cured with 1, 4-bis (aminomethyl) cyclohexane |
US3256226A (en) * | 1965-03-01 | 1966-06-14 | Robertson Co H H | Hydroxy polyether polyesters having terminal ethylenically unsaturated groups |
US3595969A (en) * | 1966-03-09 | 1971-07-27 | Princeton Chemical Res Inc | Anaerobic adhesive composition |
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 |
US3564074A (en) * | 1966-11-28 | 1971-02-16 | Dow Chemical Co | Thermosetting vinyl resins reacted with dicarboxylic acid anhydrides |
US3466259A (en) * | 1966-12-15 | 1969-09-09 | Dow Chemical Co | Thickened thermosetting vinyl ester resins |
SU549150A1 (en) | 1967-09-14 | 1977-03-05 | Composition for filling teeth | |
CH557674A (en) | 1968-05-15 | 1975-01-15 | Espe Pharm Praep | MATERIAL FOR THE PRODUCTION OF FILLINGS AND DENTAL REPLACEMENT PARTS. |
US3539533A (en) * | 1968-06-14 | 1970-11-10 | Johnson & Johnson | Dental filling material |
CA878004A (en) | 1968-06-14 | 1971-08-10 | Ii Henry L. Lee | Dental filling package |
US3754054A (en) * | 1968-12-23 | 1973-08-21 | Mitsubishi Rayon Co | Radiation curable coating compositions and process for the preparation thereof |
US3586527A (en) * | 1969-08-04 | 1971-06-22 | Ford Motor Co | Tetravinyl-unsaturated resin paint composition and painting process |
US3634542A (en) * | 1969-08-04 | 1972-01-11 | Shell Oil Co | Unsaturated polyesters esterified with polycarboxylic acid anhydride and containing polyepoxide |
US3845056A (en) | 1970-01-29 | 1974-10-29 | Union Carbide Corp | Piperazinalkyl diacrylates |
CH529559A (en) | 1970-03-10 | 1972-10-31 | Pennwalt Corp | Composition for the preparation of a dental cement |
US3673558A (en) * | 1970-05-04 | 1972-06-27 | Ciba Ltd | Polyaddition products and process for their manufacture |
US3709866A (en) * | 1970-06-01 | 1973-01-09 | Dentsply Int Inc | Photopolymerizable dental products |
GB1360910A (en) * | 1971-02-10 | 1974-07-24 | Showa Highpolymer | Resinous composition |
GB1381123A (en) | 1971-03-11 | 1975-01-22 | Shell Int Research | Process for curing epoxy resins |
CH545778A (en) | 1971-03-26 | 1974-02-15 | ||
US3769336A (en) * | 1971-05-24 | 1973-10-30 | Lee Pharmaceuticals | Polyethylene glycol diacrylate |
US3815239A (en) * | 1972-01-13 | 1974-06-11 | H Lee | Method of filling and sealing developmental pit and fissures |
US3853962A (en) * | 1972-02-03 | 1974-12-10 | Johnson & Johnson | Novel methacrylate monomer |
US3845009A (en) * | 1972-02-03 | 1974-10-29 | Johnson & Johnson | Cement compositions employing novel methacrylate monomer |
US3835090A (en) * | 1972-02-03 | 1974-09-10 | Johnson & Johnson | Dental restorative cement compositions |
US3889385A (en) * | 1972-02-11 | 1975-06-17 | Emery W Dougherty | Liquid dental opaquer and method |
US3742949A (en) * | 1972-02-14 | 1973-07-03 | C Hill | Syringe assembly |
US3980483A (en) * | 1972-04-24 | 1976-09-14 | Nippon Oil Seal Industry Co., Ltd. | Photocurable composition |
GB1461597A (en) | 1973-05-15 | 1977-01-13 | Ucb Sa | Unsaturated compounds and compositions containing them |
AT339523B (en) * | 1973-09-21 | 1977-10-25 | Jenaer Glaswerk Schott & Gen | CERAMIC GLASS FOR FULL DENTALS |
GB1464250A (en) * | 1973-12-27 | 1977-02-09 | Ciba Geigy Ag | Acrylate derivatives and their use as anaerobically-curing adhesives |
DE2406557C3 (en) * | 1974-02-12 | 1981-02-19 | Kulzer & Co Gmbh, 6380 Bad Homburg | Hydroxyl group-containing diesters of acrylic acids and dental filling material containing them |
SU545353A1 (en) | 1975-03-04 | 1977-02-05 | Composition for filling teeth | |
US4097569A (en) * | 1975-06-23 | 1978-06-27 | Youngstown Sheet And Tube Company | Modified vinyl ester resin and pipe made therefrom |
DE2534012C3 (en) * | 1975-07-30 | 1981-05-14 | Bayer Ag, 5090 Leverkusen | Process for the production of binders |
US4097994A (en) * | 1975-11-24 | 1978-07-04 | Monsanto Company | Dental restorative composition containing oligomeric BIS-GMA resin and Michler's ketone |
US4051195A (en) * | 1975-12-15 | 1977-09-27 | Celanese Polymer Specialties Company | Polyepoxide-polyacrylate ester compositions |
US4100045A (en) * | 1975-12-29 | 1978-07-11 | The Dow Chemical Company | Radiation curable epoxy coating composition of dimer acid modified vinyl ester resin |
CA1107751A (en) | 1976-01-07 | 1981-08-25 | Gerhardt P. Werber | Anaerobic monomers and adhesives |
DE2612843B2 (en) | 1976-03-26 | 1979-10-31 | Dynamit Nobel Ag, 5210 Troisdorf | Bis-acrylic esters and bis-methacrylic esters, processes for the preparation of these compounds and their use |
JPS5330193A (en) * | 1976-08-31 | 1978-03-22 | Kuraray Co | Human body hard tissue adhesive compostion |
US4187383A (en) | 1976-12-28 | 1980-02-05 | Union Carbide Corporation | Process for producing low color residue acrylate esters |
US4187382A (en) | 1976-12-28 | 1980-02-05 | Union Carbide Corporation | Process for producing low color residue acrylate ester monomers |
US4150012A (en) * | 1977-01-21 | 1979-04-17 | Minnesota Mining And Manufacturing Company | Discernible dental sealant |
US4098735A (en) * | 1977-02-14 | 1978-07-04 | Mobil Oil Corporation | Water reducible epoxy ester using monocarboxylic acid to control molecular weight |
US4135868A (en) * | 1977-04-05 | 1979-01-23 | Herbert Schainholz | Supports for instrument sterilization |
US4284742A (en) * | 1977-04-28 | 1981-08-18 | The B. F. Goodrich Company | Puncture-sealing tire |
DE2728764A1 (en) * | 1977-06-25 | 1979-01-18 | Bayer Ag | FORMULATED DENTAL FILLING MATERIALS |
US4104257A (en) | 1977-07-27 | 1978-08-01 | The Dow Chemical Company | Process for preparing high molecular weight polyether resins from bisphenols and epoxy resins |
US4141865A (en) * | 1977-10-06 | 1979-02-27 | The Dow Chemical Company | Catalysts for reaction of carboxylic acids with polyepoxides |
US4182833A (en) * | 1977-12-07 | 1980-01-08 | Celanese Polymer Specialties Company | Cationic epoxide-amine reaction products |
CH631341A5 (en) * | 1978-09-27 | 1982-08-13 | Behring Horst | CONTAINER FOR DENTAL INSTRUMENTS FOR ROOT TREATMENT. |
CH637150A5 (en) | 1978-10-30 | 1983-07-15 | Ciba Geigy Ag | EPOXY RESIN MOLDING. |
US4220582A (en) * | 1979-01-03 | 1980-09-02 | Lee Pharmaceuticals | Dental restorative compositions of improved X-ray opacity |
US4362889A (en) * | 1979-02-09 | 1982-12-07 | The American Dental Association Health Foundation | Use of a polyfunctional surface-active comonomer and other agents to improve adhesion between a resin or composite material and a substrate |
US4197390A (en) * | 1979-02-22 | 1980-04-08 | Shell Oil Company | Thickenable thermosetting vinyl ester resins |
US4368889A (en) | 1979-03-05 | 1983-01-18 | Reker Jr Louis M | Game apparatus for simulating school experience |
DD141677A1 (en) | 1979-03-15 | 1980-05-14 | Hoerhold Hans Heinrich | METHOD FOR PRODUCING HIGH-MOLECULAR THERMOPLASTIC EPOXY-AMINE POLYADDUCTS |
US4229559A (en) | 1979-05-01 | 1980-10-21 | Union Carbide Corporation | Novel bis(half ester) and compositions containing the same |
US4253830A (en) * | 1979-06-08 | 1981-03-03 | North Pacific Dental, Inc. | Autoclavable dental bur block |
US4256910A (en) | 1979-09-06 | 1981-03-17 | The B. F. Goodrich Company | Liquid reactive polymers |
US4296004A (en) * | 1979-09-10 | 1981-10-20 | Henkel Corporation | Polycyclic polyamines |
US4229376A (en) | 1979-09-10 | 1980-10-21 | Henkel Corporation | Polycyclic polyamines |
US4255468A (en) * | 1979-10-12 | 1981-03-10 | H. B. Fuller Company | Method of marking paved surfaces and curable two-part epoxy systems therefor |
US4293074A (en) * | 1979-12-04 | 1981-10-06 | Dunsky Joel L | Root canal equipment packaging |
US4595734A (en) * | 1980-02-04 | 1986-06-17 | Interplastic Corporation | Molding compositions |
FR2478650A1 (en) * | 1980-03-24 | 1981-09-25 | Commissariat Energie Atomique | CEMENT FOR USE IN FIXING BONE PROSTHESES |
CA1219990A (en) | 1980-06-09 | 1987-03-31 | Ronald S. Bauer | Saturated epoxy resin compositions exhibiting improved gloss retention |
DE3070209D1 (en) * | 1980-07-23 | 1985-03-28 | Blendax Werke Schneider Co | Adducts from diisocyanates and methacryloylalkylethers, -alcoxybenzenes resp. -alcoxycycloalcanes and their use |
US4366108A (en) | 1980-07-25 | 1982-12-28 | Ciba-Geigy Corporation | Liquid matrix system based on a mixture of epoxide resin and an amine curing agent for producing fibre-reinforced plastics components |
US4308085A (en) * | 1980-07-28 | 1981-12-29 | Jenoptik Jena Gmbh | Process for the preparation of high molecular thermoplastic epoxide-amine-polyadducts |
US4406625A (en) * | 1980-09-15 | 1983-09-27 | Scientific Pharmaceuticals, Inc. | Adducts of 1,4-bis[(3-Methacroyl-2-hydroxypropoxy)methyl]cyclohexane and derivatives thereof with isocyanates |
US4319049A (en) | 1980-10-06 | 1982-03-09 | Henkel Corporation | Bis hydroxymethyl tricyclo (5,2,1,02,6) decane |
EP0053442B2 (en) | 1980-12-03 | 1993-05-19 | Imperial Chemical Industries Plc | Dental compositions |
US4384853B1 (en) * | 1981-04-09 | 1993-11-09 | Dentsply Research & Development Corp. | Ejector holder for capsule-like cartridge |
US4391590A (en) * | 1981-04-09 | 1983-07-05 | Dentsply Research & Development Corp. | Cartridge for viscous material |
US4774063A (en) * | 1981-04-20 | 1988-09-27 | Mdt Biologic Company | Container for use with sterilizers |
US4936775A (en) * | 1981-05-04 | 1990-06-26 | Dentsply Research & Development, Corp. | Dental adhesive system |
EP0065020B1 (en) * | 1981-05-15 | 1986-03-05 | Dow Chemical Rheinwerk GmbH | Stabilized thermosettable ethylenically unsaturated epoxy ester resin compositions |
US4435497A (en) | 1981-06-19 | 1984-03-06 | Ciba-Geigy Corporation | Carboxyl-containing compositions and their polymerization |
US4569662A (en) * | 1981-10-26 | 1986-02-11 | Dragan William B | Bulk cartridge for packaging and dispensing a dental material |
US4431421A (en) * | 1981-10-28 | 1984-02-14 | Kanebo, Ltd. | Dental restorative composition |
DE3273225D1 (en) * | 1981-11-13 | 1986-10-16 | Lingner & Fischer Gmbh | Curing compositions |
US4412056A (en) | 1981-12-22 | 1983-10-25 | Shell Oil Company | Polyglycidyl ethers, their preparation and use in curable compositions |
US4514342A (en) * | 1982-02-16 | 1985-04-30 | Dentsply Limited | Polyethylenically unsaturated monophosphates |
SU1050706A1 (en) | 1982-04-07 | 1983-10-30 | 1-Й Ленинградский Ордена Трудового Красного Знамени Медицинский Институт Им.И.П.Павлова | Filling composition |
GB2123003B (en) | 1982-06-07 | 1985-09-18 | Ciba Geigy Ag | Hydroxyl terminated polyfunctional epoxy curing agents |
JPS5921646A (en) | 1982-06-25 | 1984-02-03 | Nippon Kayaku Co Ltd | Ethylenically unsaturated compound and preparation thereof |
US4405766A (en) * | 1982-07-30 | 1983-09-20 | The Dow Chemical Company | Phosphonium bicarbonate catalysts for promoting reaction of epoxides with carboxylic acids or anhydrides |
US4446246A (en) * | 1982-09-09 | 1984-05-01 | Three Bond Co., Ltd. | Catalyst systems for two-pack acrylic adhesive formulations |
NZ205522A (en) | 1982-09-13 | 1987-04-30 | Dow Chemical Co | Process for preparing glycidyl derivatives of compounds having at least one aromatic amine or hydroxy group |
US4579904A (en) * | 1982-09-24 | 1986-04-01 | Blendax Werke R. Schneider Gmbh & Co. | Diacrylic and dimethacrylic esters and their use |
GB8331151D0 (en) | 1982-12-06 | 1983-12-29 | Ici Plc | Aromatic oligomers and resins |
US4578504A (en) | 1983-06-03 | 1986-03-25 | Minnesota Mining And Manufacturing Company | Acrylate and methacrylate monomers and polymers |
US4541992A (en) * | 1983-08-10 | 1985-09-17 | Hu-Friedy Manufacturing Co. | Apparatus for organizing, sterilizing, and maintaining medical/dental instruments |
GB8322710D0 (en) * | 1983-08-24 | 1983-09-28 | Shell Int Research | Preparing aqueous binder composition |
US4548689A (en) * | 1983-09-28 | 1985-10-22 | Mitsui Petrochemical Industries, Ltd. | Photocurable resin composition |
USRE35135E (en) | 1983-09-28 | 1995-12-26 | Mitsui Petrochemical Industries, Ltd. | Photocurable resin composition |
US4515634A (en) * | 1983-10-17 | 1985-05-07 | Johnson & Johnson Dental Products Company | Castable glass-ceramic composition useful as dental restorative |
US4557848A (en) * | 1983-12-08 | 1985-12-10 | Texaco Inc. | Crankcase lubricant |
US5137990A (en) | 1984-02-28 | 1992-08-11 | Shell Oil Company | Heat-curable polyepoxide-(meth)acrylate ester compositions |
GB8411731D0 (en) | 1984-05-09 | 1984-06-13 | Unilever Plc | Oral compositions |
IL75191A (en) | 1984-05-14 | 1988-10-31 | Ici Plc | Aromatic oligomers and dental products and photoresists prepared therefrom |
CA1276648C (en) | 1984-07-19 | 1990-11-20 | Rafael L. Bowen | Method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates |
US4535148A (en) | 1984-08-01 | 1985-08-13 | Henkel Corporation | Polyglycidyl ethers of tricyclodecane and cured epoxy resins therefrom |
US4547531A (en) * | 1984-08-02 | 1985-10-15 | Pentron Corporation | Two component (paste-paste) self-curing dental restorative material |
EP0182744B1 (en) | 1984-11-14 | 1992-08-12 | Ciba-Geigy Ag | Radiation curable filled epoxy resin compositions and their use |
US4657941A (en) * | 1984-11-29 | 1987-04-14 | Dentsply Research & Development Corp. | Biologically compatible adhesive containing a phosphorus adhesion promoter and a sulfinic accelerator |
AU578924B2 (en) | 1984-12-12 | 1988-11-10 | Sankin Kogyo Kabushiki Kaisha | Tooth restoration composition having x-ray contrastability |
DE3447355A1 (en) * | 1984-12-24 | 1986-07-03 | Basf Ag, 6700 Ludwigshafen | CROSSLINKABLE RESIN, LIGHT SENSITIVE RECORDING MATERIAL BASED ON THIS CROSSLINKABLE RESIN AND METHOD FOR PRODUCING A FLAT PRINTING PLATE BY MEANS OF THIS LIGHT SENSITIVE RECORDING MATERIAL |
DE3502594A1 (en) | 1985-01-26 | 1986-07-31 | Etablissement Dentaire Ivoclar, Schaan | X-RAY OPAQUE DENTAL MATERIAL |
US4713482A (en) | 1985-03-26 | 1987-12-15 | Ciba-Geigy Corporation | Maleic or phthalic acid half esters of alkoxylated fatty amines |
US4874799A (en) * | 1985-05-17 | 1989-10-17 | M&T Chemicals Inc. | Aqueous akaline developable, UV curable urethane acrylate compounds and compositions useful for forming liquid 100 percent solids, solvent-free solder mask coatings |
JPS61268610A (en) * | 1985-05-24 | 1986-11-28 | G C Dental Ind Corp | Dental adherent resin composition |
DE3682537D1 (en) | 1985-06-06 | 1992-01-02 | Ciba Geigy Ag | POLYEPOXIDES AND THEIR USE. |
EP0205402B1 (en) | 1985-06-06 | 1990-05-23 | Ciba-Geigy Ag | 2,6-disubstituted-4-epoxypropylphenyl glycidyl ethers, and their preparation |
DE3522005A1 (en) | 1985-06-20 | 1987-01-02 | Bayer Ag | (METH) ACRYLIC ACID ESTERS AND THEIR USE |
US4854475A (en) * | 1985-07-22 | 1989-08-08 | Hu-Friedy Manufacturing Co., Inc. | Instrument cassette |
IT1190382B (en) | 1985-07-26 | 1988-02-16 | Montedison Spa | ACRYLIC DIHESTERS FOR BISPHENOL ALCHYL ETHER, RELATED POLYMERS AND COMPOSITES FOR DENTAL USE |
DE3536076A1 (en) | 1985-10-09 | 1987-04-09 | Muehlbauer Ernst Kg | POLYMERIZABLE CEMENT MIXTURES |
DE3536077A1 (en) | 1985-10-09 | 1987-04-09 | Muehlbauer Ernst Kg | POLYMERIZABLE ACID AND ACID DERIVATIVES COMPOUNDS, MIXTURES CONTAINING THE SAME AND THEIR USE |
US4643303A (en) * | 1985-10-15 | 1987-02-17 | Micromedics, Inc. | Modular sterilizing system |
JPS62161742A (en) * | 1986-01-08 | 1987-07-17 | Nippon Paint Co Ltd | Terminal carboxyl group-containing reactive acrylic monomer and production thereof |
US4789620A (en) * | 1986-03-03 | 1988-12-06 | Mitsubishi Rayon Co. Ltd. | Liquid photosensitive resin composition containing carboxylated epoxy acrylates or methacrylates |
US4816528A (en) * | 1986-06-23 | 1989-03-28 | E. I. Dupont De Nemours And Company | Chip resistant coating compositions containing epoxy-polyester graft copolymers |
DE3621039A1 (en) | 1986-06-24 | 1988-01-07 | Bayer Ag | METHOD FOR PRODUCING OLIGOESTERS HAVING HYDROXYL GROUPS AND THE USE THEREOF |
US4781921A (en) * | 1986-10-06 | 1988-11-01 | The University Of Akron | Hydrogels of quadrol methacrylate polymers |
KR950003688B1 (en) | 1986-10-30 | 1995-04-17 | 미쓰이세끼유 가가꾸 고오교오 가부시끼가이샤 | Curable coposition |
SU1510131A1 (en) | 1986-11-21 | 1991-02-15 | 1-Й Московский Медицинский Институт Им.И.М.Сеченова | Composition filling root canals of teeth |
US4767326A (en) * | 1986-11-25 | 1988-08-30 | Dentsply Research & Development Corp. | Cartridge container and ejector piston therefor |
US5106301A (en) | 1986-12-26 | 1992-04-21 | G-C Dental Industrial Corp. | Method for inspecting the root canal with a radiopaque impression material |
JPS63165302A (en) | 1986-12-26 | 1988-07-08 | G C Dental Ind Corp | Contrasting impression material for root canal inspection |
US5178851A (en) | 1987-01-30 | 1993-01-12 | Colgate-Palmolive Company | Antiplaque antibacterial oral composition |
JPS63268780A (en) | 1987-04-28 | 1988-11-07 | G C Dental Ind Corp | Dentin bonding compound |
DE3730921A1 (en) * | 1987-09-15 | 1989-03-23 | Degussa | HITZEHAERTBARE DENTAL MASSES |
US4964911A (en) * | 1987-10-13 | 1990-10-23 | Den-Mat Corporation | Adhesive bonding of acrylic resins, especially in dentistry |
US4863993A (en) * | 1987-12-09 | 1989-09-05 | Opi Products, Inc. | Surface priming composition for proteinaceous substrates; method of making and using same |
US5129825A (en) | 1987-12-21 | 1992-07-14 | Discko John Jr | Dental syringe and capsule for use therewith |
JPH01294609A (en) * | 1988-02-09 | 1989-11-28 | Toyo Kagaku Kenkyusho:Kk | Dental sealer for root canal filling |
US4959199A (en) * | 1988-02-19 | 1990-09-25 | Brewer Charles A | Autoclavable modular cassette and tray for holding dental instruments |
US4918136A (en) * | 1988-03-28 | 1990-04-17 | Tokuyama Soda Kabushiki Kaisha | Adhesive composition |
US5160737A (en) | 1988-05-03 | 1992-11-03 | Perio Products Ltd. | Liquid polymer composition, and method of use |
US4950697A (en) * | 1988-09-15 | 1990-08-21 | Block Drug Co., Inc. | Thermoplastic and injectable endodontic filling compositions |
US5052927A (en) | 1988-10-24 | 1991-10-01 | Discko John Jr | Syringe and disposable capsule with cannula for use therewith |
NL8802683A (en) | 1988-11-02 | 1990-06-01 | Philips Nv | METHOD FOR JOINING TWO BODIES WITH AN ADHESIVE AND A COMPOSITE BODY. |
JPH0667816B2 (en) | 1988-11-11 | 1994-08-31 | 株式会社クラレ | Dental restorative |
JPH02138106A (en) | 1988-11-18 | 1990-05-28 | Jishi Toushi Kogyo Kk | Photopolymerization type resin composition for dentistry |
JP2813825B2 (en) | 1988-12-19 | 1998-10-22 | テラ‐ゲゼルシャフト フィアー パテントフェルヴェルツング ミット ベシュレンクテル ハフツング | Dental compositions containing bifunctional acrylates or methacrylates |
DE3843938A1 (en) | 1988-12-24 | 1990-06-28 | Henkel Kgaa | METHOD FOR IMPROVED PRODUCTION OF (METH) ACRYLIC ACIDES OF PRESCRIBED ALCOHOLS (II) |
DE3843930A1 (en) | 1988-12-24 | 1990-06-28 | Henkel Kgaa | METHOD FOR IMPROVED PRODUCTION OF (METH) ACRYLIC ACIDES OF PRECIOUS ALCOHOLS (III) |
DE3843854A1 (en) | 1988-12-24 | 1990-06-28 | Henkel Kgaa | METHOD FOR IMPROVED PRODUCTION OF (METH) ACRYLIC ACIDES OF PRESCRIBED ALCOHOLS (I) |
DE3843843A1 (en) | 1988-12-24 | 1990-07-05 | Henkel Kgaa | METHOD FOR IMPROVED PRODUCTION OF (METH) ACRYLIC ACIDES OF PRESCRIBED ALCOHOLS (IV) |
US4910329A (en) | 1989-01-11 | 1990-03-20 | Rohm And Haas Company | Process for preparing hydroxyalkyl esters |
EP0429556B1 (en) | 1989-01-27 | 1996-09-11 | Neil Rex Hall | Reinforced composite resin |
US4963093A (en) * | 1989-02-06 | 1990-10-16 | Dragan William B | Dental syringe tip and syringe holder therefor |
DE3903407A1 (en) | 1989-02-06 | 1990-08-09 | Blendax Werke Schneider Co | DENTAL FUELING MATERIAL |
USD315956S (en) | 1989-02-06 | 1991-04-02 | Dragan William B | Dental syringe tip |
US5083921A (en) | 1989-02-06 | 1992-01-28 | Dragan William B | Dental syringe tip |
US5028638A (en) | 1989-02-09 | 1991-07-02 | Bayer Aktiengesellschaft | Hybrid plastic filling material |
US5006066A (en) | 1989-02-17 | 1991-04-09 | Rouse Melvin R | Autoclavable dental burr holder |
US4975055A (en) | 1989-03-02 | 1990-12-04 | A-Dec, Inc. | Flexible conduit structure for dental appliances |
US5084491A (en) | 1989-03-16 | 1992-01-28 | The Ohio University | Reinforcing glass ionomer dental filling material with stainless steel, or metals thereof |
US4969816A (en) | 1989-03-20 | 1990-11-13 | Melvin Drumm | Dental material carrier and applicator |
CA2012824A1 (en) | 1989-03-22 | 1990-09-22 | Marian D. Sullivan | Swag centerpiece with taper candle/chimney glass insert |
US4948848A (en) | 1989-04-07 | 1990-08-14 | Gaf Chemicals Corporation | Solution feed, slurry polymerization process for the production of copolymers of maleic anhydride and an alkyl vinyl ether having predetermined specific viscosities |
DE3911929A1 (en) | 1989-04-12 | 1990-10-18 | Hoechst Ag | AMPHIPHILES MONOMERS AND POLYMERS AND FILM OF AT LEAST ONE MONOMOLECULAR LAYER THEREOF |
JPH02279615A (en) | 1989-04-20 | 1990-11-15 | Mitsubishi Rayon Co Ltd | Adhesive composition for dental use |
US5169267A (en) | 1989-05-03 | 1992-12-08 | Cowper Norman T | Method of pumping coal slurries |
FR2647794B1 (en) | 1989-06-02 | 1991-09-27 | Norsolor Sa | METHOD AND SYSTEM FOR PRIMING ANIONIC POLYMERIZATION OF (METH) ACRYLATES |
ATE121104T1 (en) | 1989-06-05 | 1995-04-15 | Atochem Elf Sa | PROCESS AND ANIONIC POLYMERIZATION CATALYSTS FOR ACRYLATE MONOMERS. |
US4889900A (en) | 1989-06-12 | 1989-12-26 | Shell Oil Company | Preparation of alkyl methacrylate monomers for anionic polymerization |
US5210157A (en) | 1989-08-15 | 1993-05-11 | Akzo N.V. | Interpenetrating network of ring-containing allyl polymers and epoxy resin, and a laminate prepared therefrom |
JP2780722B2 (en) | 1989-10-02 | 1998-07-30 | 三井化学株式会社 | Acrylic copolymer, its production method and its use |
FR2653036B1 (en) | 1989-10-17 | 1992-01-10 | Inst Francais Du Petrole | CATALYTIC COMPOSITION COMPRISING TITANIUM AND PHOSPHORUS, ITS PREPARATION AND ITS USE FOR THE CONDENSATION OF AN EPOXIDE ON A CARBOXYLIC ACID ANHYDRIDE. |
DE3937265A1 (en) | 1989-11-09 | 1991-05-16 | Metallgesellschaft Ag | SORTING METHOD AND DEVICE |
AU644618B2 (en) | 1989-12-28 | 1993-12-16 | G-C Shika Kogyo Kabushiki Kaisha | Odontotherapeutical materials |
EP0436382B1 (en) | 1990-01-03 | 1994-04-06 | Minnesota Mining And Manufacturing Company | Dental material containing anti-slump additive |
US5100320A (en) | 1990-01-16 | 1992-03-31 | Minnesota Mining And Manufacturing Company | Dental packaging material and cartridge |
CA2035650C (en) | 1990-02-14 | 1997-02-25 | Hajime Yasuda | Process of preparing polymer or copolymer of unsaturated carboxylic acid ester |
CA2041828A1 (en) | 1990-03-05 | 1992-11-04 | Richard L. Lindstrom | Viscoelastic solution |
DE4008696A1 (en) | 1990-03-17 | 1991-09-19 | Basf Ag | METHOD FOR THE PRODUCTION OF HOMO- AND COPOLYMERISES OF MONOETHYLENICALLY DISPRODUCED DICARBONE ACIDS AND THEIR USE |
CA2026417C (en) | 1990-03-28 | 1996-07-02 | Atsufumi Manabe | Dental adhesives |
US5032669A (en) | 1990-05-01 | 1991-07-16 | University Of Massachusetts At Amherst | Liquid crystalline polyesters formed by reaction of bis(hydroxyalkoxy) biphenyls with terephthaloyl chloride |
FR2663926B1 (en) | 1990-06-27 | 1994-04-15 | Norsolor | NOVEL ACRYLATE CYCLES WITH ALCOHOL, ALDEHYDE AND / OR ETHER FUNCTION, MANUFACTURING METHOD THEREOF AND APPLICATION THEREOF TO OBTAIN NEW POLYMERS AND COPOLYMERS. |
FR2664272B3 (en) | 1990-07-06 | 1992-11-27 | Norsolor | PROCESS FOR THE SELECTIVE EPOXIDATION OF UNSATURATED (METH) ACRYLATES, NEW FUNCTIONAL (METH) ACRYLATES OBTAINED AND THEIR APPLICATION TO THE SYNTHESIS OF NEW POLYMERS. |
US5235008A (en) | 1990-08-03 | 1993-08-10 | The Dow Chemical Company | Polymer modified adducts of epoxy resins and active hydrogen containing compounds containing mesogenic moieties |
HUT58266A (en) | 1990-08-31 | 1992-02-28 | Hoechst Celanese Corp | Acrylic esters of 1,1,1-tris/hydroxy-phenyl/-ethane, process for producing them, utilizing them as monofunctional polymerizable monomere and homo-and copolymeres from them |
JPH0819173B2 (en) | 1990-09-14 | 1996-02-28 | テルモ株式会社 | Polymerization initiator composition for controlling polymerization at interface and curable composition containing the same |
CA2026467A1 (en) | 1990-09-28 | 1992-03-29 | Ralph G. Moyer | Intertube thermal conductance rate limiting device |
US5173273A (en) | 1990-10-11 | 1992-12-22 | Brewer Charles A | Cassette for dental instruments |
US5171763A (en) | 1990-12-14 | 1992-12-15 | Tokuyama Soda Kabushiki Kaisha | Curable composition |
US5165890A (en) | 1991-01-07 | 1992-11-24 | Centrix, Inc. | Dosing dental cartridge |
US5267859A (en) | 1991-01-07 | 1993-12-07 | Centrix, Inc. | Bulk dental cartridge |
US5122057A (en) | 1991-01-07 | 1992-06-16 | Centrix, Inc. | Dosing dental cartridge |
GB2255781B (en) | 1991-02-15 | 1995-01-18 | Reactive Ind Inc | Adhesive system |
DE4105550A1 (en) | 1991-02-22 | 1992-08-27 | Bayer Ag | ADHESIVE COMPONENT FOR TREATING THE DENTAL SUBSTANCE |
DE4109048A1 (en) | 1991-03-15 | 1992-09-17 | Tech Hochschule C Schorlemmer | Modified epoxy-(meth)acrylate(s) for prods. with low water absorption - obtd. by esterification of epoxide oligomers, e.g. bisphenol=A di:glycidyl ether, with (meth)acrylic acid and satd. mono:carboxylic acid |
JP3034650B2 (en) | 1991-06-19 | 2000-04-17 | 株式会社ジーシー | Tooth adhesive |
US5294413A (en) | 1991-07-17 | 1994-03-15 | Hu-Friedy Mfg. Co., Inc. | Sterilization and storage cassette |
US5215726A (en) | 1991-07-17 | 1993-06-01 | Hu-Friedy Mfg. Co., Inc. | Two-tiered sterilization and storage cassette |
US5108287A (en) | 1991-09-05 | 1992-04-28 | Nancy Yee | Autoclavable drill bit container |
US5236362A (en) | 1991-10-11 | 1993-08-17 | Essential Dental Systems, Inc. | Root canal filling material and adhesive composition |
US5172810A (en) | 1991-11-06 | 1992-12-22 | Brewer Charles A | Receptacle for holding dental burrs |
CA2086770A1 (en) | 1992-01-10 | 1993-07-11 | Jyi-Faa Hwang | Epoxy interpenetrating polymer networks having internetwork bonds |
USD353673S (en) | 1992-02-27 | 1994-12-20 | Centrix, Inc. | Combined dental syringe tip and a sealing cap |
US5204398A (en) | 1992-03-17 | 1993-04-20 | Essential Dental Systems, Inc. | Composite dental cement composition containing a lanthanide series compound |
US5384103A (en) | 1992-03-17 | 1995-01-24 | Micromedics, Inc. | Instrument tray |
DE4217761A1 (en) | 1992-05-29 | 1993-12-02 | Univ Schiller Jena | â, þ-methacrylate-terminated epoxy-carboxylic acid macromonomers |
US5346677A (en) | 1992-09-04 | 1994-09-13 | Risk William B | Instrument cassette |
US5217372A (en) | 1992-09-17 | 1993-06-08 | Truocchio Michael A | Dentistry practice |
US5324273A (en) | 1992-09-30 | 1994-06-28 | Centrix, Inc. | Disposable barrel dental impression material syringe |
US5322440A (en) | 1992-10-20 | 1994-06-21 | Kerr Manufacturing Company | Dental syringe tip |
US5279800A (en) | 1992-11-25 | 1994-01-18 | C/T Med-Systems Ltd., Inc. | Dental cassette kit |
DE19525941C2 (en) * | 1995-07-18 | 1999-11-25 | Ivoclar Ag Schaan | Polymerizable liquid-crystalline monomer, dental materials based on liquid-crystalline monomers and use of a polymerizable monomer with liquid-crystalline properties for the production of a dental material |
-
1996
- 1996-10-07 US US08/723,443 patent/US5998499A/en not_active Expired - Fee Related
- 1996-10-16 EP EP96936465A patent/EP0861230B1/en not_active Expired - Lifetime
- 1996-10-16 DE DE69618661T patent/DE69618661T2/en not_active Expired - Fee Related
- 1996-10-16 WO PCT/US1996/016436 patent/WO1997014674A1/en active IP Right Grant
- 1996-10-16 JP JP51590897A patent/JP2001509128A/en not_active Withdrawn
- 1996-10-16 CA CA002229379A patent/CA2229379A1/en not_active Abandoned
-
1999
- 1999-09-08 US US09/391,539 patent/US6339114B1/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0379058A2 (en) * | 1989-01-17 | 1990-07-25 | The Dow Chemical Company | Vinyl ester resins containing mesogenic/rigid rodlike moieties |
EP0675186A1 (en) * | 1994-03-30 | 1995-10-04 | F. Hoffmann-La Roche AG | Photo-curable liquid crystals |
Non-Patent Citations (2)
Title |
---|
HOELTER D ET AL: "Liquid Crystalline Thermosets Based on Branched Bismethacrylates", MACROMOLECULES (MAMOBX,00249297);96; VOL.29 (22); PP.7003-7011, ALBERT-LUDWIGS-UNIVERSITAET;INSTITUT FUER MAKROMOLEKULARE CHEMIE; FREIBURG I. BR.; D-79104; GERMANY (DE), XP000614231 * |
MORTON H. LITT: "Crosslinked Liqid Crystal Polymers from Liquid Crystal Monomers: Synthesis and Mechanical Properties", J. POLYMER SCIENCE, PART A: POLYMER CHEMISTRY, vol. 31, no. 1, 1993, NEW YORK, pages 183 - 191, XP000331766 * |
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6258974B1 (en) | 1993-04-13 | 2001-07-10 | Southwest Research Institute | Metal oxide compositions composites thereof and method |
US6410765B1 (en) | 1993-04-13 | 2002-06-25 | Southwest Research Institute | Methods of making functionalized nanoparticles |
US6417244B1 (en) | 1993-04-13 | 2002-07-09 | Southwest Research Institute | Metal oxide compositions and methods |
US6695617B1 (en) | 1993-04-13 | 2004-02-24 | Southwest Research Institute | Methods of dental repair using functionalized nanoparticles |
US6696585B1 (en) | 1993-04-13 | 2004-02-24 | Southwest Research Institute | Functionalized nanoparticles |
US6743936B1 (en) | 1993-04-13 | 2004-06-01 | Southwest Research Insittute | Composites made using functionalized nanoparticles |
JPH1121269A (en) * | 1997-06-30 | 1999-01-26 | Dainippon Ink & Chem Inc | Liquid-crystal (meth)acrylate compound, liquid-crystal composition, and optical an isotropic body using the same compound |
US7238831B2 (en) | 2001-01-23 | 2007-07-03 | Southwest Research Institute | Mesogens |
US7108801B2 (en) | 2001-01-23 | 2006-09-19 | Southwest Reasearch Institute | Methods and blends for controlling rheology and transition temperature of liquid crystals |
US7094358B2 (en) | 2001-03-07 | 2006-08-22 | The University Of Texas System | Ultra-low shrinkage composite resins based on blended nematic liquid crystal monomers |
US7135589B2 (en) | 2001-03-07 | 2006-11-14 | Board Of Regents, The University Of Texas System | Bridged monomers |
US9522133B2 (en) | 2008-07-23 | 2016-12-20 | Arena Pharmaceuticals, Inc. | Substituted 1,2,3,4-tetrahydrocyclopenta[b]indol-3-yl)acetic acid derivatives useful in the treatment of autoimmune and inflammatory disorders |
US8580841B2 (en) | 2008-07-23 | 2013-11-12 | Arena Pharmaceuticals, Inc. | Substituted 1,2,3,4-tetrahydrocyclopenta[b]indol-3-yl)acetic acid derivatives useful in the treatment of autoimmune and inflammatory disorders |
US9126932B2 (en) | 2008-07-23 | 2015-09-08 | Arena Pharmaceuticals, Inc. | Substituted 1,2,3,4-tetrahydrocyclopenta[b]indol-3-yl)acetic acid derivatives useful in the treatment of autoimmune and inflammatory disorders |
US8415484B2 (en) | 2008-08-27 | 2013-04-09 | Arena Pharmaceuticals, Inc. | Substituted tricyclic acid derivatives as S1P1 receptor agonists useful in the treatment of autoimmune and inflammatory disorders |
US9108969B2 (en) | 2008-08-27 | 2015-08-18 | Arena Pharmaceuticals, Inc. | Substituted tricyclic acid derivatives as S1P1 receptor agonists useful in the treatment of autoimmune and inflammatory disorders |
US8853419B2 (en) | 2010-01-27 | 2014-10-07 | Arena Pharmaceuticals, Inc. | Processes for the preparation of (R)-2-(7-(4-cyclopentyl-3-(trifluoromethyl)benzyloxy)-1,2,3,4-tetrahydrocyclopenta[b]indol-3-yl)acetic acid and salts thereof |
US9175320B2 (en) | 2010-01-27 | 2015-11-03 | Arena Pharmaceuticals, Inc. | Processes for the preparation of (R)-2-(7-4-cyclopentyl-3-(trifluoromethyl)benzyloxy)-1,2,3,4-tetrahydrocyclopenta[B]indol-3-yl)acetic acid and salts thereof |
US9447041B2 (en) | 2010-01-27 | 2016-09-20 | Arena Pharmaceuticals, Inc. | Processes for the preparation of (R)-2-(7-4-cyclopentyl-3-(trifluoromethyl)benzyloxy)-1,2,3,4-tetrahydrocyclopenta[B]indol-3-yl)acetic acid and salts thereof |
US11149292B2 (en) | 2010-01-27 | 2021-10-19 | Arena Pharmaceuticals, Inc. | Processes for the preparation of (R)-2-(7-(4-cyclopentyl-3-(trifluoromethyl)benzyloxy)-1,2,3,4-tetrahydrocyclopenta[B]indol-3-yl)acetic acid and salts thereof |
US11674163B2 (en) | 2010-01-27 | 2023-06-13 | Arena Pharmaceuticals, Inc. | Processes for the preparation of (R)-2-(7-(4-cyclopentyl-3-(trifluoromethyl)benzyloxy)-1,2,3,4-tetrahydrocyclopenta[b]indol-3-yl)acetic acid and salts thereof |
US9085581B2 (en) | 2010-03-03 | 2015-07-21 | Arena Pharmaceuticals, Inc. | Processes for the preparation of S1P1 receptor modulators and crystalline forms thereof |
US11007175B2 (en) | 2015-01-06 | 2021-05-18 | Arena Pharmaceuticals, Inc. | Methods of treating conditions related to the S1P1 receptor |
US11896578B2 (en) | 2015-01-06 | 2024-02-13 | Arena Pharmaceuticals, Inc. | Methods of treating conditions related to the S1P1 receptor |
US11091435B2 (en) | 2015-06-22 | 2021-08-17 | Arena Pharmaceuticals, Inc. | Crystalline L-arginine salt of (R)-2-(7-(4-cyclopentyl-3-(trifluoromethyl)benzyloxy)-1,2,3, 4-tetrahydrocyclo-penta [b]indol-3-yl)acetic acid(compound1) for use in S1P1 receptor-associated disorders |
US10676435B2 (en) | 2015-06-22 | 2020-06-09 | Arena Pharmaceuticals, Inc. | Crystalline L-arginine salt of (R)-2-(7-(4-cyclopentyl-3-(trifluoromethyl)benzyloxy)-1,2,3,4-tetrahydrocyclo-penta [b]indol-3-yl)acetic acid(Compound 1) for use in SIPI receptor-associated disorders |
US10301262B2 (en) | 2015-06-22 | 2019-05-28 | Arena Pharmaceuticals, Inc. | Crystalline L-arginine salt of (R)-2-(7-(4-cyclopentyl-3-(trifluoromethyl)benzyloxy)-1,2,3,4-tetrahydrocyclo-penta [b]indol-3-yl)acetic acid(Compund1) for use in SIPI receptor-associated disorders |
US11884626B2 (en) | 2015-06-22 | 2024-01-30 | Arena Pharmaceuticals, Inc. | Crystalline L-arginine salt of (R)-2-(7-(4-cyclopentyl-3-(trifluoromethyl)benzyloxy)-1,2,3,4-tetrahydrocyclo-penta [b]indol-3-yl)acetic acid(Compound1) for use in S1P1 receptor-associated disorders |
US11478448B2 (en) | 2017-02-16 | 2022-10-25 | Arena Pharmaceuticals, Inc. | Compounds and methods for treatment of inflammatory bowel disease with extra-intestinal manifestations |
US11534424B2 (en) | 2017-02-16 | 2022-12-27 | Arena Pharmaceuticals, Inc. | Compounds and methods for treatment of primary biliary cholangitis |
US11555015B2 (en) | 2018-09-06 | 2023-01-17 | Arena Pharmaceuticals, Inc. | Compounds useful in the treatment of autoimmune and inflammatory disorders |
Also Published As
Publication number | Publication date |
---|---|
DE69618661D1 (en) | 2002-02-28 |
DE69618661T2 (en) | 2002-09-26 |
US6339114B1 (en) | 2002-01-15 |
EP0861230B1 (en) | 2002-01-02 |
EP0861230A1 (en) | 1998-09-02 |
CA2229379A1 (en) | 1997-04-24 |
US5998499A (en) | 1999-12-07 |
JP2001509128A (en) | 2001-07-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0861230B1 (en) | Liquid crystalline (meth)acrylate compounds, composition and method | |
US5276068A (en) | Dental resin materials | |
EP0323521B1 (en) | Curable composition | |
EP0120559B1 (en) | Adhesive | |
US6031015A (en) | Dental materials based on liquid crystalline monomers | |
US7541392B2 (en) | Materials leading to improved dental composites and dental composites made therefrom | |
US20060058415A1 (en) | Materials leading to improved dental composites and dental composites made therefrom | |
US20050124762A1 (en) | Dental compositions containing core-shell polymers with low modulus cores | |
EP1879544B1 (en) | Materials and dental composites made therefrom | |
CA2202755C (en) | Polymerizable compounds and compositions | |
US20050124721A1 (en) | Bulky monomers leading to resins exhibiting low polymerization shrinkage | |
US20060058418A1 (en) | Materials leading to improved dental composites and dental composites made therefrom | |
US20060058417A1 (en) | Materials leading to improved dental composites and dental composites made therefrom | |
JP2865794B2 (en) | Adhesive composition | |
JP2002531476A (en) | Dental composition | |
US7560500B2 (en) | Materials leading to improved dental composites and dental composites made therefrom | |
JP3549427B2 (en) | Vinylcyclopropane- (meth) acrylate and uses thereof | |
US20050124722A1 (en) | Branched highly-functional monomers exhibiting low polymerization shrinkage | |
WO2005056623A1 (en) | Dental compositions containing liquids and other elastomers | |
US7495038B2 (en) | Materials leading to improved dental composites and dental composites made therefrom | |
US6353061B1 (en) | α, ω-methacrylate terminated macromonomer compounds | |
EP2881103B1 (en) | Dental composition | |
JPH0513123B2 (en) | ||
JPS6172705A (en) | Dental material | |
JPH0422904B2 (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CA JP |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
ENP | Entry into the national phase |
Ref document number: 2229379 Country of ref document: CA Ref country code: CA Ref document number: 2229379 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1996936465 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 1997 515908 Kind code of ref document: A Format of ref document f/p: F |
|
WWP | Wipo information: published in national office |
Ref document number: 1996936465 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 1996936465 Country of ref document: EP |